Comprehensive Experimental and Computational Spectroscopic Study of Hexacyanoferrate Complexes in Water: From Infrared to X-ray Wavelengths

Ross, Matthew,Andersen, Amity,Fox, Zachary W.,Zhang, Yu,Hong, Kiryong,Lee, Jae-Hyuk,Cordones, Amy,March, Anne Marie,Doumy, Gilles,Southworth, Stephen H.,Marcus, Matthew A.,Schoenlein, Robert W.,Mukame American Chemical Society 2018 The journal of physical chemistry. B, Condensed ma Vol.122 No.19

<P>We present a joint experimental and computational study of the hexacyanoferrate aqueous complexes at equilibrium in the 250 meV to 7.15 keV regime. The experiments and the computations include the vibrational spectroscopy of the cyanide ligands, the valence electronic absorption spectra, and Fe 1s core hole spectra using element-specific-resonant X-ray absorption and emission techniques. Density functional theory-based quantum mechanics/molecular mechanics molecular dynamics simulations are performed to generate explicit solute-solvent configurations, which serve as inputs for the spectroscopy calculations of the experiments spanning the IR to X-ray wavelengths. The spectroscopy simulations are performed at the same level of theory across this large energy window, which allows for a systematic comparison of the effects of explicit solute-solvent interactions in the vibrational, valence electronic, and core-level spectra of hexacyanoferrate complexes in water. Although the spectroscopy of hexacyanoferrate complexes in solution has been the subject of several studies, most of the previous works have focused on a narrow energy window and have not accounted for explicit solute-solvent interactions in their spectroscopy simulations. In this work, we focus our analysis on identifying how the local solvation environment around the hexacyanoferrate complexes influences the intensity and line shape of specific spectroscopic features in the UV/vis, X-ray absorption, and valence-to-core X-ray emission spectra. The identification of these features and their relationship to solute-solvent interactions is important because hexacyanoferrate complexes serve as model systems for understanding the photochemistry and photophysics of a large class of Fe(II) and Fe(III) complexes in solution.</P> [FIG OMISSION]</BR>

반자연적인 조건에서 두 계통 바퀴 (Blattella germanica)의 휴식처 체제 시간 및 방문빈도에 대한 시간적 유형

Tae-Soo CHON,Young Seuk PARK,Mary H. ROSS 한국응용곤충학회 1997 한국응용곤충학회지 Vol.36 No.4

돌연변이체인 or (orange body) 계통과 KNIH (Korea National Institute of Health) 계통의 바퀴(Blattella germanica (L.) (Orthoptera: Blattellidae)를 반자연적인 조건하에서 비디오와 컴퓨터 자료처리를 통하여 연속적으로 관찰하였다. 휴식처에 머무르거나, 먹고, 물 마시며, 다른 개체들과 교신하는 행동을 관찰 할 수 있는 사각형의 관찰상자 내에서 수컷 성충을 개체별로 4~5일 동안 연속적으로 관찰하였는데, 본 논문에서는 휴식처에 머무르는 시간과 방문 빈도를 분석하였다. 개체들 간의 변이가 상대적으로 컸지만 시험개체들은 휴식처에 전체 관찰시간의 47 -61%를 평균적으로 머무르는 것으로 나타났다. 판찰 개체가 휴식처에서 머무르는 시간은 모계에 따른 유의한 차이가 있었으나, 계통 사이에는 뚜렷하게 구분이 되지 않았다. 명암기의 차이는 두 계통 모두 관찰되었는데 휴식처에 머무르는 시간은 암기보다 명기에서 더 길었다. 휴식처 주변의 국소적 활동성을 나타내주는 방문빈도는 KNIH 계통보다 or 계통에서 상대적으로 높게 나타났는데, 모계와 계통간에 유의한 차이가 있었다. 방문빈도의 명암기 차이는 or 계통에서는 유의하게 나타났지만 KNIH 계통에서는 없었다. 개체들 간의 변이가 있었으나 동일한 모계 내에서 휴식처에 머무르는 시간이나 방문빈도가 유사하게 관찰되는 개체들이 있었다. A mutant, or(orange body), and the KNIH(Korea National Institute of Health) strain of the German cockroach, Blattella germanica(L.) (Orthoptera: Blattellidae), were observed continuously in semi-natural conditions through video taping and data processing by computers. Male adults were individually observed for 4-5 days in a rectangular-shaped rearing cage with four different microhabitats, allowing observations of behavior such as resting, feeding, drinking and communicating with other individuals. The frequencies of visits to and times spent within harborage were determined. Although there were relatively large variations among individuals, the average stays withing harborage ranged from 47-61% of the total observation time. The duration of within-harborage time was significantly different between maternal origins, while not distinctively different between the strains. Diel differences were observed in body strains. The time spent within harborage was longer in photophase than in scotophase. visiting frequency, which represented local activity around harborage, appeared slightly higher in the or strain than in the KNIH strain, and was significant in the or strain while it was not significant in the KNIH strain. Although there were variations among individuals, similar temporal patterns in some progenies from the same maternal origins were observed in time spent within harborage and in visiting frequency.

Activity of the German Cockroach, Blattella germanica(L.) (Orthoptera: Blattellidae), at Different Microhabitats in Semi-natural Conditions when Treated with Sublethal Doses of Chlorpyrifos and Permethrin

Chon, Tae-Soo,Young Seuk Park,Mary H. Ross Korean Society of Applied Entomology 1998 Journal of Asia-Pacific Entomology Vol.1 No.1

Male adults of a mutant, or(orange body), and KNIH(Korea National Institute of Health) strains of the German cockroach, Blattella germanica(L.) were individually treated with chlorpyrifos and permethrin in sublethal doses. Local activity at different microhabitats for harborage, food, water, and other neighbor cockroaches was measured by observing visiting frequency for 4~5 days continuously after the chemical treatment. Also long-range activity was observed by counting the number of crossing imaginary center-lines within the observation cage during the observation period. The local activity was generally decreased after the treatment of chemicals at most microhabitats. Trends local of the activity abserved in the control also appeared in response to the chemical treatments; local activity was the highest at harborage, and was low at the other microhabitats. The diel difference observed in the local activity, however, disappeared in the or strain by the treatment of both insecticides. Especially high values in local and long-range activity at scotophase were decreased greatly. In the KNIH strain, the local activity was less affected with chlorpyrifos. Diel difference persisted in the chlorpyrifos treatment, but disappeared in the permethrin treatment. The long-range activity was increased in the chlorpyrifos treatment in the KNIH strain.

Temporal Pattern of the Local Activity at Harborage in Two Strains of the German Cockroach, Blattella germanica (L.), in Semi- natural Conditions after Treated with Sublethal Doses of Insecticides

Chon, Tae-Soo,Park, Young-Seuk,Mary H. Ross, Mary H. Ross 한국곤충학회 1998 Entomological Research Vol.28 No.1

바퀴의 돌연변이인 or(orange body)계통과 KNIH(Korea National Institute of Health)계통의 수컷 성충을 개별적으로 chlorpyrifos와 permethrin을 아치사량 처리한 후, 쉴 곳, 먹이, 물, 이웃 바퀴가 공급된 반 자연적인 조건에서 4~5일 연속적으로 관찰하였다. 개체변이가 상대적으로 심했지만, 약제처리 후 쉼터에서의 체재시간이나 방문빈도는 대체적으로 감소하였다. 그러나 or계통에서 permethrin이 처리되었을 때, 처리 후 쉼터에서의 체재시간은 별반 감소하지 않았고, 방문빈도도 암기에서는 감소한 반면 명기에서는 큰 변이가 없었다. 전체적으로 체재시간이나 방문빈도의 일 변이에 대한 약제 처리의 영향은 크게 관찰되지 않았다. After male adults of a mutant, or (orange body), and a KNIH (Korea National Institute of Health) strain of the German cockroach, Blattella germanica (L.), had been treated individually with chlorpyrifos and permethrin in sublethal doses, they were observed continuously for 4~5 days in semi- natural conditions, providing harborage, food, water and other individuals. Although individual variation was relatively high, visiting frequency and within-harborage time were generally decreased with the treatment of the insecticides. With the permethrin treatment to the or strain, however, within-harborage time was not decreased clearly, and visiting frequency in photophase remained in the similar level while it was decreased in scotophase. Generally diel differences in within-harborage time and visiting frequency were not greatly affected by the treatment of the insecticides.

Temporal Pattern of the Local Activity at Harborage in Two Strains of the German Cockroach, Blattella germanica(L.), in Semi-natural Conditions after Treated with Sublethal Doses of Insecticides

CHON, Tae-Soo,PARK, Young Seuk,ROSS, Mary H. 부산대학교 유전공학연구소 1998 분자생물학 연구보 Vol.14 No.-

바퀴의 돌연변이인 or(orange body)계통과 KNIH(Korean National Institute of Health)계통의 수컷 성충을 개별적으로 chorpyrifos와 permethrin을 아치사량 처리한 후, 쉴 곳, 먹이, 물, 이웃 바퀴가 공급된 반 자연적인 조건에서 4∼5일 연속적으로 관찰하였다. 개체변이가 상대적으로 심했지만, 약제처리 후 쉼터에서의 체재시간이나 방문빈도는 대체적으로 감소하였다. 그러나 or계통에서 permethrin이 처리되었을 때, 처리 후 쉼터에서의 체재시간은 별반 감소하지 않았고, 방문빈도도 암기에서는 감소한 반면 명기에서는 큰 변이가 없었다. 전체적으로 체재시간이나 방문빈도의 일변이에 대한 약제 처리의 영향은 크게 관찰되지 않았다. After male adults of a mutant, or(orange body), and a KNIH(Korean National Institute of Health)strain of the German Cockroach, Blattella germanica(L.), had been treated individually with chorpyrifos and permethrin in subethal doses, they were observed continuously for 4∼5 days in semi-natural conditions, providing harborage, food, water and other individuals. Although individual variation was relatively high, visiting frequency and within-harborage time were generally decreased with the treatment of the insecticides. With the permethrin treatment to the or strain, however, within-harborage times was decreased clearly, and visiting frequency in photophase remained in the similar level while it was decreased in scotophase. Generally diel differences in within-harborage time and visiting frequency were not greatly affected by the treat-ment of the insecticides.

Activity of the German Cockroach, Blattella germanica(L.) (Orthoptera: Blattellidae), at Different Microhabitats in Semi-natural Conditions when Treated with Sublethal Doses of Chlorpyrifos and Permethrin

Chon, Tae-Soo,Park, Young Seuk,Ross, Mary H. 부산대학교 유전공학연구소 1998 분자생물학 연구보 Vol.14 No.-

Male adults of a mutant, or (orange body), and KNIH(Korea National Institute of Health) strains of the German cockroach, Blattella germanica(L.), were individually treated with chlorpyrifos and permethrin in sublethal doses. Local activity at different microhabitats for harborage, food, water, and other neighbor cockroaches was measured by observing visiting frequency for 4∼5 days continuously after the chemical treatment. Also long-range activity was observed by counting the number of crossing imaginary center-lines within the observation cage during the observation period. The local activity was generally decreased after the treatment of chemicals at most microhabitats. Trends of the activity observed in the control also appeared in response to the chemical treatment, local activity was the highest at harborage, and was low at the other microhabitats. The diel difference observed in the local activity, however, disappeared in the or strain by the treatment of both insecticides. Especially high values in local and long-range activity at scotophase were decreased greatly. In the KNIH strain, the local activity was less affected with chlorpyrifos. Diel difference persisted in the chlorpyrifos treatment, but disappeared in the permethrin treatment. The long-range activity was increased in the chlorpyrifos treatment in the KNIH strain.