Intermediate Spectra Research Articles

Reactivity of neonicotinoid insecticides with carbonate radicals

The reaction of three chloronicotinoid insecticides, namely Imidacloprid (IMD), Thiacloprid (THIA) and Acetamiprid (ACT), with carbonate radicals (CO3−) was investigated. The second order rate constants (4 ± 1) × 106, (2.8 ± 0.5) × 105, and (1.5 ± 1) × 105 M−1 s−1 were determined for IMD, THIA and ACT, respectively. The absorption spectra of the organic intermediates formed after CO3− attack to IMD is in line with those reported for α-aminoalkyl radicals. A reaction mechanism involving an initial charge transfer from the amidine nitrogen of the insecticides to CO3− is proposed and further supported by the identified reaction products. The pyridine moiety of the insecticides remains unaffected until nicotinic acid is formed. CO3− radical reactivity towards IMD, ACT, and THIA is low compared to that of HO• radicals, excited triplet states, and 1O2, and is therefore little effective in depleting neonicotinoid insecticides.

THE YOUNG OPEN CLUSTER BERKELEY 55

We present UBV photometry of the highly reddened and poorly studied open cluster Berkeley 55, revealing an important population of B-type stars and several evolved stars of high luminosity. Intermediate resolution far-red spectra of several candidate members confirm the presence of one F-type supergiant and six late supergiants or bright giants. The brightest blue stars are mid-B giants. Spectroscopic and photometric analyses indicate an age 50+-10 Myr. The cluster is located at a distance d~4kpc, consistent with other tracers of the Perseus Arm in this direction. Berkeley 55 is thus a moderately young open cluster with a sizable population of candidate red (super)giant members, which can provide valuable information about the evolution of intermediate-mass stars.

Undetectable role of oxidative DNA damage in cell cycle, cytotoxic and clastogenic effects of Cr(VI) in human lung cells with restored ascorbate levels

Cultured human cells are invaluable biological models for mechanistic studies of genotoxic chemicals and drugs. Continuing replacement of animals in toxicity testing will further increase the importance of in vitro cell systems, which should accurately reproduce key in vivo characteristics of toxicants such as their profiles of metabolites and DNA lesions. In this work, we examined how a common severe deficiency of cultured cells in ascorbate (Asc) impacts the formation of oxidative DNA damage by hexavalent chromium (chromate). Cr(VI) is reductively activated inside the cells by both Asc and small thiols but with different rates and spectra of intermediates and DNA adducts. We found that Cr(VI) exposure of H460 human lung epithelial cells in standard culture (<0.01 mM cellular Asc) induced biologically significant amounts of oxidative DNA damage. Inhibition of oxidative damage repair in these cells by stable XRCC1 knockdown strongly enhanced cytotoxic effects of Cr(VI) and led to depletion of cells from G(1) and accumulation in S and G(2) phases. However, restoration of physiological levels of Asc (≈ 1 mM) completely eliminated Cr(VI) hypersensitivity of XRCC1 knockdown. The induction of chromosomal breaks assayed by the micronucleus test in Asc-restored H460, primary human lung fibroblasts, and CHO cells was also unaffected by the XRCC1 status. Centromere-negative (clastogenic) micronuclei accounted for 80-90% of all Cr(VI)-induced micronuclei. Consistent with the micronuclei results, Asc-restored cells also showed no increase in the levels of poly(ADP-ribose), which is a biochemical marker of single-stranded breaks. Asc had no effect on cytotoxicity of O(6)-methylguanine, a lesion produced by direct DNA alkylation. Overall, our results indicate that the presence of physiological levels of Asc strongly suppresses pro-oxidant pathways in Cr(VI) metabolism and that the use of standard cell cultures creates a distorted profile of its genotoxic properties.

Low temperature FTIR spectroscopy provides new insights in the pH-dependent proton pathway of proteorhodopsin

In the presented study the low pH photocycle of proteorhodopsin is extensively investigated by means of low temperature FTIR spectroscopy. Besides the already well-known characteristics of the all-trans and 13-cis retinal vibrations the 77K difference spectrum at pH 5.1 shows an additional negative signal at 1744cm−1 which is interpreted as indicator for the L state. The subsequent photocycle steps are investigated at temperatures higher than 200K. The combination of visible and FTIR spectroscopy enabled us to observe that the deprotonation of the Schiff base is linked to the protonation of an Asp or Glu side chain — the new proton acceptor under acidic conditions. The difference spectra of the late intermediates are characterized by large amide I changes and two further bands ((−)1751cm−1/(+)1725cm-1) in the spectral region of the Asp/Glu ν(C=O) vibrations. The band position of the negative signature points to a transient deprotonation of Asp-97. In addition, the pH dependence of the acidic photocycle was investigated. The difference spectra at pH 5.5 show distinct differences connected to changes in the protonation state of key residues. Based on our data we propose a three-state model that explains the complex pH dependence of PR.

Infrared and visible absolute and difference spectra of bacteriorhodopsin photocycle intermediates.

We have used new kinetic fitting procedures to obtain infrared (IR) absolute spectra for intermediates of the main bacteriorhodopsin (bR) photocycle(s). The linear-algebra-based procedures of Hendler et al. (J. Phys. Chem. B, 105, 3319-3228 (2001)) for obtaining clean absolute visible spectra of bR photocycle intermediates were adapted for use with IR data. This led to isolation, for the first time, of corresponding clean absolute IR spectra, including the separation of the M intermediate into its M(F) and M(S) components from parallel photocycles. This in turn permitted the computation of clean IR difference spectra between pairs of successive intermediates, allowing for the most rigorous analysis to date of changes occurring at each step of the photocycle. The statistical accuracy of the spectral calculation methods allows us to identify, with great confidence, new spectral features. One of these is a very strong differential IR band at 1650 cm(-1) for the L intermediate at room temperature that is not present in analogous L spectra measured at cryogenic temperatures. This band, in one of the noisiest spectral regions, has not been identified in any previous time-resolved IR papers, although retrospectively it is apparent as one of the strongest L absorbance changes in their raw data, considered collectively. Additionally, our results are most consistent with Arg82 as the primary proton-release group (PRG), rather than a protonated water cluster or H-bonded grouping of carboxylic residues. Notably, the Arg82 deprotonation occurs exclusively in the M(F) pathway of the parallel cycles model of the photocycle.

Modelling the high-mass accretion rate spectra of GX 339−4: black hole spin from reflection?

We extract all the XMM-Newton EPIC pn burst mode spectra of GX 339-4, together with simultaneous/contemporaneous RXTE data. These include three disc dominated and two soft intermediate spectra, and the combination of broad bandpass/moderate spectral resolution gives some of the best data on these bright soft states in black hole binaries. The disc dominated spectra span a factor three in luminosity, and all show that the disc emission is broader than the simplest multicolour disc model. This is consistent with the expected relativistic smearing and changing colour temperature correction produced by atomic features in the newest disc models. However, these models do not match the data at the 5 per cent level as the predicted atomic features are not present in the data, perhaps indicating that irradiation is important even when the high energy tail is weak. Whatever the reason, this means that the data have smaller errors than the best physical disc models, forcing use of more phenomenological models for the disc emission. We use these for the soft intermediate state data, where previous analysis using a simple disc continuum found an extremely broad residual, identified as the red wing of the iron line from reflection around a highly spinning black hole. However, the iron line energy is close to where the disc and tail have equal fluxes, so using a broader disc continuum changes the residual 'iron line' profile dramatically. With a broader disc continuum model, the inferred line is formed outside of 30 ${\rm{R_g}}$, so cannot constrain black hole spin. We caution that a robust determination of black hole spin from the iron line profile is very difficult where the disc makes a significant contribution at the iron line energy i.e. in most bright black hole states.

Product-assisted Catalysis as the Basis of the Reaction Specificity of Threonine Synthase

Threonine synthase (TS), which is a pyridoxal 5'-phosphate (PLP)-dependent enzyme, catalyzes the elimination of the γ-phosphate group from O-phospho-L-homoserine (OPHS) and the subsequent addition of water at Cβ to form L-threonine. The catalytic course of TS is the most complex among the PLP enzymes, and it is an intriguing problem how the elementary steps are controlled in TS to carry out selective reactions. When L-vinylglycine was added to Thermus thermophilus HB8 TS in the presence of phosphate, L-threonine was formed with k(cat) and reaction specificity comparable with those when OPHS was used as the substrate. However, in the absence of phosphate or when sulfate was used in place of phosphate, only the side reaction product, α-ketobutyrate, was formed. Global analysis of the spectral changes in the reaction of TS with L-threonine showed that compared with the more acidic sulfate ion, the phosphate ion decreased the energy levels of the transition states of the addition of water at the Cβ of the PLP-α-aminocrotonate aldimine (AC) and the transaldimination to form L-threonine. The x-ray crystallographic analysis of TS complexed with an analog for AC gave a distinct electron density assigned to the phosphate ion derived from the solvent near the Cβ of the analog. These results indicated that the phosphate ion released from OPHS by γ-elimination acts as the base catalyst for the addition of water at Cβ of AC, thereby providing the basis of the reaction specificity. The phosphate ion is also considered to accelerate the protonation/deprotonation at Cγ.

Tsallis-Pareto like distributions in hadron-hadron collisions

Non-extensive thermodynamics is a novel approach in high energy physics. In high-energy heavy-ion, and especially in proton-proton collisions we are far from a canonical thermal state, described by the Boltzmann-Gibbs statistic. In these reactions low and intermediate transverse momentum spectra are extremely well reproduced by the Tsallis-Pareto distribution, but the physical origin of Tsallis parameters is still an unsettled question.Here, we analyze whether Tsallis-Pareto energy distribution do overlap with hadron spectra at high-pT. We fitted data, measured in proton-proton (proton-antiproton) collisions in wide center of mass energy range from 200 GeV RHIC up to 7 TeV LHC energies. Furthermore, our test is extended to an investigation of a possible -dependence of the power in the Tsallis-Pareto distribution, motivated by QCD evolution equations. We found that Tsallis-Pareto distributions fit well high-pT data, in the wide center of mass energy range. Deviance from the fits appears at pT > 20–30 GeV/c, especially on CDF data [7]. Introducing a pT-scaling ansatz, the fits at low and intermediate transverse momenta still remain good, and the deviations tend to disappear at the highest-pT data.

Time-Resolved Resonance Raman Studies on Proton-Induced Electron-Transfer Reaction from Triplet Excited State of 2-Methoxynaphthalene to Decafluorobenzophenone

In this paper, time-resolved resonance Raman (TR3) spectra of intermediates generated by proton-induced electron-transfer reaction between triplet 2-methoxynaphthalene ((3)ROMe) and decafluorobenzophenone (DFBP) are presented. The TR3 vibrational spectra and structure of 2-methoxynaphthalene cation radical (ROMe(•+)) have been analyzed by density functional theory (DFT) calculation. It is observed that the structure of naphthalene ring of ROMe(•+) deviates from the structure of cation radical of naphthalene.

Interface doping of conjugated organic films by means of diffusion of atomic components from the surfaces of semiconductors and of metal oxides

The paper reports the results on the interface formation of 5–10 nm thick conjugated layers of Cu-phthalocyanine (CuPc) with a number of solid surfaces: polycrystalline Au, (SiO 2) n–Si, ZnO ( 0 0 0 1 ¯ ) , Si(1 0 0), Ge(1 1 1), CdS ( 0 0 0 1 ¯ ) and GaAs(1 0 0). The results were obtained using Auger electron spectroscopy (AES) and low-energy target current electron spectroscopy (TCS). The organic overlayers were thermally deposited in situ in UHV onto substrate surfaces. The island-like organic deposits were excluded from the analysis so that only uniform organic deposits were considered. In the cases of polycrystalline Au, Si(1 0 0) and Ge(1 1 1) substrates the AES peaks of the substrate material attenuated down to the zero noise level upon the increase of the CuPc film thickness of 8–10 nm. The peaks corresponding to oxygen atoms in the case of SiO 2 substrate, and to atoms from the ZnO, GaAs and CdS substrates were clearly registered in the AES spectra of the 8–10 nm thick CuPc deposits. The relative concentration of the substrate atomic components diffused into the film was different from their relative concentration at the pure substrate surface. The concentration of the substrate dopant atoms in the CuPc film was estimated as one atom per one CuPc molecule. Using the target current electron spectroscopy, it was shown that the substrate atoms admixed in the CuPc film account for the appearance of a new peak in the density of unoccupied electronic states. Formation of intermediate TCS spectra until the CuPc deposit reaches 2–3 nm was observed in the cases of GaAs(1 0 0), ZnO ( 0 0 0 1 ¯ ) , Ge(1 1 1) surfaces. The intermediate spectra show a less pronounced peak structure different from the one typical for the CuPc films. It was suggested that the intermediate layer was formed by the CuPc molecules fully or partially decomposed due to the interaction with the relatively reactive semiconductor surfaces.

Photometric and spectroscopic observations of three rapidly rotating late‐type stars: EY Dra, V374 Peg, and GSC 02038‐00293

AbstractHere, BV (RI)C broad band photometry and intermediate resolution spectroscopy in Hα region are presented for two rapidly rotating late‐type stars: EY Dra and V374 Peg. For a third rapid rotator, GSC 02038‐00293, intermediate resolution Hα spectroscopy and low resolution spectroscopy are used for spectral classification and stellar parameter investigation of this poorly known object. The low resolution spectrum of GSC 02038‐00293 clearly indicates that it is a K‐type star. Its intermediate resolution spectrum can be best fitted with a model with Teff = 4750 K and v sin i = 90 km s–1, indicating a very rapidly rotating mid‐K star. The Hα line strength is variable, indicating changing chromospheric emission on GSC 02038‐00293. In the case of EY Dra and V374 Peg, the stellar activity in the photosphere is investigated from the photometric observations, and in the chromosphere from the Hα line. The enhanced chromospheric emission in EY Dra correlates well with the location of the photospheric active regions, indicating that these features are spatially collocated. Hints of this behaviour are also seen in V374 Peg, but it cannot be confirmed from the current data. The photospheric activity patterns in EY Dra are stable during one observing run lasting several nights, whereas in V374 Peg large night‐tonight variations are seen. Two large flares, one in the Hα observations and one from the broadband photometry, and twelve smaller ones were detected in V374 Peg during the observations spanning nine nights. The energy of the photometrically detected largest flare is estimated to be 4.25 × 1031– 4.3 × 1032 erg, depending on the waveband. Comparing the activity patterns in these two stars, which are just below and above the mass limit of full convection, is crucial for understanding dynamo operation in stars with different internal structures (© 2010 WILEY‐VCH Verlag GmbH &amp; Co. KGaA, Weinheim)

Radiolysis of berberine or palmatine in aqueous solution

The reactions of hydrated electron ( e a q − ) , hydrogen atom (H ) (reducing species) and Cl 2 • − , Br 2 • − , N • 3 , O • H radicals (oxidizing species) with berberine or palmatine in aqueous solution have been studied by steady-state and pulse radiolysis. The spectra of transient intermediates, leading to the final products, are presented. The rate constants of the reaction of e a q − and OH radical with both alkaloids in the homogenous solution and in the presence of DNA are reported. It is demonstrated that the primary products of the reaction of berberine and palmatine with e a q − and radicals generated during radiolysis are unstable and undergo further reactions.

Chromospheric activity among fast-rotating M dwarfs in the open cluster NGC 2516

We report radial velocities (RVs), projected equatorial velocities (v sin i) and CaII triplet (CaT) chromospheric activity indices for 237 late-K to mid-M candidate members of the young open cluster NGC 2516. These stars have rotation periods between 0.1 and 15 days. Intermediate resolution spectra were obtained using the Giraffe spectrograph at the Very Large Telescope. Membership was confirmed on the basis of RVs for 210 targets. We see a marked increase in the fraction of rapidly rotators as we move to cooler spectral types. About 20 per cent of M0-M1 stars have v sin i >15km/s, increasing to 90 per cent of M4 stars. Activity indices derived from the first two lines of the CaT (8498A and 8542A) show differing dependencies on rotation period and mass for stars lying above and below the fully convective boundary. Higher mass stars, of spectral type K3-M2.5, show chromospheric activity which increases with decreasing Rossby number (the ratio of period to convective turnover time), saturating for Rossby numbers <0.1. For cooler stars, which are probably fully convective and almost all of which have Rossby numbers <0.1, there is a clear decrease in chromospheric activity as (V-I)_0 increases, amounting to a fall of about a factor of 2-3 between spectral types M2.5 and M4. This decrease in activity levels at low Rossby numbers is not seen in X-ray observations of the coronae of cluster M-dwarfs or of active field M-dwarfs. There is no evidence for supersaturation of chromospheric activity for stars of any spectral type at Rossby numbers <0.01. We suggest that the fall in the limiting level of chromospheric emission beyond spectral type M3 in NGC~2516 is, like the simultaneous increase in rotation rates in field stars, associated with a change in the global magnetic topology as stars approach the fully convective boundary and not due to any decrease in dynamo-generated magnetic flux.

Morphological and phytochemical variation, genetic structure and phenology in an introgressive hybrid swarm of Senecio hercynicus and S. ovatus (Compositae, Senecioneae)

Introgressive hybridisation between Senecio hercynicus and Senecio ovatus (Compositae, Senecioneae) was studied in a mixed stand of the two species on the S- and SW-facing slopes of the German part of the Bohemian Forest (SE Germany). Morphological variation based on multivariate analysis of 14 diagnostic characters, along with genetic data from an amplified fragment length polymorphism (AFLP) fingerprinting analysis, indicates that the surveyed stand forms an intensively introgressed hybrid swarm. The majority of individuals were found to be intermediate between the two parental taxa, and strong statistical correlation between phenetic and genetic distances was observed. In contrast to that, flowering time of individuals (expressed as the time when 50% of the capitula of a plant were in flower) was found to follow a bimodal distribution in the hybrid swarm and lacked any correlation with the genetic and morphological relationships among plants. The same was true for the spectra of pyrrolizidine alkaloids (PA) revealed by a gas-chromatographic survey: most of the 142 individuals surveyed fell into one of two main chemotypes, only a few plants exhibited an intermediate and additive PA spectrum, and no correlation with the genetic and morphological relationships among plants was observed. Assuming that most of the AFLP markers are neutral, we conclude that the correlation of morphology with the genetic pattern may argue for the neutrality of morphological features analysed. Consequently, we interpret the lack of correlation between phenological and phytochemical data with the neutral genetic markers as evidence that both phenology and phytochemistry may be either under selection or that these features are genetically or biosynthetically constrained.

Intermediate frequency Raman spectra of defective single‐walled carbon nanotubes

AbstractWe simulated Raman spectra of defective single‐walled carbon nanotubes within a non‐orthogonal tight‐binding model. The creation of defects in the nanotubes effectively lowers their symmetry and makes a large number of phonons Raman‐active. The Raman spectra of such nanotubes will be similar in shape to their phonon density of states (PDOS). Assuming that for a low density of defects the change of the PDOS is negligible with respect to that of perfect nanotubes, we used the latter as an approximation of the former. The Raman scattering from perfect nanotubes is essentially resonant. Similarly to above, neglecting the change of the electronic structure due to a low density of defects, we adopted the same resonance conditions for defective nanotubes as for perfect ones. Based on these assumptions, we modeled the resonant Raman spectra of a sample of defective nanotubes by means of the PDOS of perfect nanotubes. The obtained results can be used for interpretation of experimental Raman spectra of defective nanotube samples.

Porphyrin on a Half-Shell! Synthesis and Characterization of Corannulenoporphyrins

An efficient synthetic method for preparing corannulenoporphyrins is described. Nitrocorannulene was reacted with ethyl isocyanoacetate in the presence of a phosphazene base to generate the pivotal corannulenopyrrole intermediate. Following cleavage of the ethyl ester moiety with KOH in ethylene glycol at 180-190 degrees C, the heptacyclic system was reacted with acetoxymethylpyrroles under mildly acidic conditions to afford tripyrranes. The proton NMR spectra for these tripyrrolic intermediates suggest that they can take on helical geometries, but the conformations are dependent on the nature of the terminal ester groupings and may be altered by solvent interactions. Treatment of a di-tert-butyl ester tripyrrane with TFA cleaved the protective groups, and subsequent condensation with diformylpyrroles in TFA-CH(2)Cl(2), followed by oxidation with DDQ or ferric chloride, gave excellent yields of corannulenoporphyrins. Nickel(II), copper(II), and zinc complexes of this system were also prepared, and the nickel derivative was also further characterized by X-ray crystallography. The same synthetic strategy was also used to prepare a porphyrin with fused acenaphthylene and corannulene subunits. The fused bowl-shaped corannulene provides these porphyrins with a unique structural component that increases solubility by reducing pi-pi stacking interactions.

Electronic absorption spectra of photoreaction intermediates of 7-hydroxyquinoline monomer in a low-temperature argon matrix and time-dependent density-functional-theory calculations

Abstract Photoreaction of 7-hydroxyquinoline monomer in a low-temperature argon matrix was investigated, and electronic absorption spectra of three unstable species generated by UV-light irradiation were measured. By comparison with the calculated spectral patterns obtained by the time-dependent density-functional-theory calculation, the electronic absorption bands around 460, 360 and 260 nm appearing after UV irradiation were assigned, respectively, to the keto form produced from the enol form of 7-hydroxyquinoline by migration of the hydrogen atom of the OH group to the N atom, quinolinoxyl radical by elimination of a hydrogen atom, and 7-ketene by Wolff rearrangement following elimination of a hydrogen molecule.

Deciphering Excited State Evolution in Halorhodopsin with Stimulated Emission Pumping

The primary photochemical dynamics of Hb. pharaonis Halorhodopsin (pHR) are investigated by femtosecond visible pump-near IR dump-hyperspectral probe spectroscopy. The efficiency of excited state depletion is deduced from transient changes in absorption, recorded with and without stimulated emission pumping (SEP), as a function of the dump delay. The concomitant reduction of photocycle population is assessed by probing the "K" intermediate difference spectrum. Results show that the cross section for stimulating emission is nearly constant throughout the fluorescent state lifetime. Probing "K" demonstrates that dumping produces a proportionate reduction in photocycle yields. We conclude that, despite its nonexponential internal conversion (IC) kinetics, the fluorescent state in pHR constitutes a single intermediate in the photocycle. This contrasts with conclusions drawn from the study of primary events in the related chloride pump from Hb. salinarum (sHR), believed to produce the "K" intermediate from a distinct short-lived subpopulation in the excited state. Our discoveries concerning internal conversion dynamics in pHR are discussed in light of recent expectations for similar excited state dynamics in both proteins.

Enzymatic and electron paramagnetic resonance studies of anabolic pyruvate synthesis by pyruvate: ferredoxin oxidoreductase from Hydrogenobacter thermophilus

Pyruvate: ferredoxin oxidoreductase (POR; EC 1.2.7.1) catalyzes the thiamine pyrophosphate-dependent oxidative decarboxylation of pyruvate to form acetyl-CoA and CO(2). The thermophilic, obligate chemolithoautotrophic hydrogen-oxidizing bacterium, Hydrogenobacter thermophilus TK-6, assimilates CO(2) via the reductive tricarboxylic acid cycle. In this cycle, POR acts as pyruvate synthase catalyzing the reverse reaction (i.e. reductive carboxylation of acetyl-CoA) to form pyruvate. The pyruvate synthesis reaction catalyzed by POR is an energetically unfavorable reaction and requires a strong reductant. Moreover, the reducing equivalents must be supplied via its physiological electron mediator, a small iron-sulfur protein ferredoxin. Therefore, the reaction is difficult to demonstrate in vitro and the reaction mechanism has been poorly understood. In the present study, we coupled the decarboxylation of 2-oxoglutarate catalyzed by 2-oxoglutarate: ferredoxin oxidoreductase (EC 1.2.7.3), which generates sufficiently low-potential electrons to reduce ferredoxin, to drive the energy-demanding pyruvate synthesis by POR. We demonstrate that H. thermophilus POR catalyzes pyruvate synthesis from acetyl-CoA and CO(2), confirming the operation of the reductive tricarboxylic acid cycle in this bacterium. We also measured the electron paramagnetic resonance spectra of the POR intermediates in both the forward and reverse reactions, and demonstrate the intermediacy of a 2-(1-hydroxyethyl)- or 2-(1-hydroxyethylidene)-thiamine pyrophosphate radical in both reactions. The reaction mechanism of the reductive carboxylation of acetyl-CoA is also discussed.

Spectroscopic Investigation of the Multiphoton Photolysis Reactions of Bromomethanes (CHBr3, CHBr2Cl, CHBrCl2, and CH2Br2) at Near-Ultraviolet Wavelengths

Nascent emission and laser-induced dispersed fluorescence spectra of products or intermediates from the multiphoton photolysis reaction of bromomethanes (CHBr(3), CHBr(2)Cl, CHBrCl(2), and CH(2)Br(2)) at 266 nm were recorded in a slow flow cell. Electronically excited species including CH (A(2)Delta, B(2)Sigma(-), and C(2)Sigma(+)), C(2) (d(3)Pi(g)), and atomic Br ((4)D(J) and (4)P(J)) were observed in the nascent emission spectra. Free radicals such CHBr or CHCl were also successfully found using laser-induced dispersed fluorescence spectroscopy. The reactive intermediate, CHBr, was seen only in the photolysis of CHBr(3), whereas CHCl was only discovered when the precursor was CHBr(2)Cl or CHBrCl(2). More experiments including the power dependence and temporal waveform measurements were conducted. The present study reports the first direct measurements of the intermediate products in the multiphoton photodissociation reaction of these bromomethanes at 266 nm. Nascent emission spectra following the photolysis at longer near-ultraviolet wavelengths (280 and 355 nm) were also acquired. On the bassis of these results, the multiphoton photodissociation mechanism of these bromomethanes at 266 nm can be confirmed.