Preface ...................................................... XVII
About the Editors ............................................. XIX
List of Contributors for Both Volumes ....................... XXIII
Part Three Active Surfaces .................................... 315
18 The Genesis and Principle of Catalysis at Oxide
Surfaces: Surface-Mediated Dynamic Aspects of Catalytic
Dehydration and Dehydrogenation on TiO2(110) by STM and
DFT ....................................................... 317
Yohei Uemura, Toshiaki Taniike, Takehiko Sasaki, Mizuki
Tada, and Yasuhiro Iwasawa
18.1 Introduction ........................................ 317
18.2 Experimental ........................................ 318
18.2.1 STM Measurements of TiO2(110) ............... 318
18.2.2 Computational Methods ....................... 318
18.3 Results and Discussion .............................. 319
18.3.1 Dynamic Mechanism for Catalytic Dehydration
of Formic Acid on a TiO2(110) Surface, Much
Different from the Traditional Static Acid
Catalysis ................................... 319
18.3.2 Dynamic Catalytic Dehydrogenation of Formic
Acid on a TiO2(HO) Surface .................. 327
18.3.2.1 Mechanism of the Switchover of
Reaction Paths .................... 331
18.4 Conclusion and Perspective .......................... 332
References .......................................... 333
19 Nuclear Wavepacket Dynamics at Surfaces ................... 337
Kazuya Watanabe
19.1 Introduction ........................................ 337
19.2 Experimental Techniques ............................. 338
19.2.1 Time-Resolved Two-Photon Photoemission with
Femtosecond Laser Pulses .................... 338
19.2.1.1 Principles ........................ 338
19.2.1.2 Experimental Set-Up ............... 339
19.2.2 Time-Resolved Second Harmonic Generation .... 340
19.2.2.1 Principles and Brief History ...... 340
19.2.2.2 Experimental Set-Up ............... 341
19.3 Nuclear Wavepacket Motions of Adsorbate Probed by
Time-Resolved 2PPE .................................. 343
19.3.1 Alkali Atom Desorption from a Metal
Surface ..................................... 343
19.3.2 Solvation Dynamics at Metal Surfaces ........ 344
19.3.3 Ultrafast Proton-Coupled Electron Transfer
at Interfaces ............................... 345
19.4 Nuclear Wavepacket Motion at Surfaces Probed by
Time-Resolved SHG ................................... 345
19.4.1 Vibrational Coherence and Coherent Phonons
at Alkali-Covered Metal Surfaces ............ 345
19.4.2 Dephasing of the Vibrational Coherence:
Excitation Fluence Dependence ............... 347
19.4.3 Excitation Mechanisms ....................... 349
19.4.4 Mode Selective Excitation of Coherent
Surface Phonons ............................. 351
19.5 Concluding Remarks .................................. 352
References .......................................... 353
20 Theoretical Aspects of Charge Transfer/Transport at
Interfaces and Reaction Dynamics .......................... 357
Hisao Nakamura and Koichi Yamashita
20.1 Introduction and Theoretical Concepts ............... 357
20.1.1 Introduction ................................ 357
20.1.2 Molecular Orbital Theory and Band Theory .... 358
20.1.3 Charge Transfer vs. Charge Transport ........ 359
20.1.4 Electronic Excitation ....................... 361
20.1.5 Reaction Dynamics ........................... 363
20.2 Electrode-Molecule -Electrode Junctions ............. 365
20.2.1 Nonequilibrium Green's Function Formalism ... 365
20.2.2 Efficient MO Approach ....................... 367
20.2.3 Ab Initio Calculations: Single Molecular
Conductance and Waveguide Effects ........... 370
20.2.4 Inelastic Transport and Inelastic Electron
Tunneling Spectroscopy ...................... 375
20.3 Photochemistry on Surfaces .......................... 381
20.3.1 Theoretical Model of Hot Electron Transport
and Reaction Probability .................... 381
20.3.2 Photodesorption Mechanism of Nitric Oxide on
an Ag(III) Surface .......................... 384
20.4 Summary and Outlook ................................. 392
References .......................................... 394
21 Dynamic Behavior of Active Ag Species in NOx Reduction
on Ag/Al2O3 ............................................... 401
Atsushi Satsuma and Ken-ichi Shimizu
21.1 Introduction ........................................ 401
21.1.1 NOx Reduction Technologies for Diesel and
Lean-Burn Gasoline Engines .................. 401
21.1.2 Selective Catalytic Reduction of NOx by
Hydrocarbons Over Ag/Al2O3 .................. 402
21.2 Hydrogen Effect of HC-SCR Over Ag/Al2O3 ............. 403
21.2.1 Boosting of HC-SCR Activity of Ag/Al2O3 by
Addition of H2 .............................. 403
21.2.2 Surface Dynamics of Ag Species Analyzed by
in situ UV-Vis .............................. 405
21.3 The Role of Surface Adsorbed Species Analyzed by
in situ FTIR ........................................ 410
21.3.1 Reaction Scheme of HC-SCR Over Ag/Al2O3 ..... 410
21.3.2 Effect of H2 Addition on Reaction Pathways
of HC-SCR Over Ag/Al2O3 ..................... 414
21.4 Relation Between Ag Cluster and Oxidative
Activation of Hydrocarbons .......................... 416
21.4.1 Debates on Role of Ag Clusters .............. 416
21.4.2 Reductive Activation of O2 and Promoted
HC-SCR on Ag Cluster ........................ 420
References .......................................... 422
22 Dynamic Structural Change of Pd Induced by Interaction
with Zeolites Studied by Means of Dispersive and Quick
XAFS ...................................................... 427
Kazu Okumura
22.1 Introduction ........................................ 427
22.2 Formation and Structure of Highly Dispersed PdO
Interacted with Brensted Acid Sites ................. 428
22.3 Energy-Dispersive XAFS Studies on the Spontaneous
Dispersion of PdO and Reversible Formation of
Stable Pd Clusters in H-ZSM-5 and H-Mordenite ....... 430
22.4 In Situ QXAFS Studies on the Dynamic Coalescence
and Dispersion Processes of Pd in USY Zeolite ....... 432
22.5 Time-Resolved EXAFS Measurement of the Stepwise
Clustering Process of Pd Clusters at Room
Temperature ......................................... 435
22.6 Summary ............................................. 438
References .......................................... 439
Part Four Single Crystals .................................... 441
23 Morphology Changes of Photochromic Single Crystals ........ 443
Seiya Kobatake and Masahiro Irie
23.1 Introduction ........................................ 443
23.2 Photochromic Diarylethene Crystals .................. 444
23.3 X-Ray Crystallographic Analysis ..................... 444
23.4 Reactivity in the Crystal ........................... 447
23.5 Photomechanical Effect .............................. 448
23.6 Crystal Surface Changes ............................. 449
23.7 Photoreversible Crystal Shape Changes ............... 450
References .......................................... 454
24 Direct Observation of Change in Crystal Structures
During Solid-State Reactions of 1,3-Diene Compounds ....... 459
Akikazu Matsumoto
24.1 Introduction ........................................ 459
24.1.1 Crystal Engineering Renaissance ............. 459
24.2 EZ-Photoisomerization ............................... 460
24.2.1 Model of Photoisomerization ................. 460
24.2.2 Photoisomerization of Benzyl Muconate ....... 462
24.2.3 Change in Crystal Structures During
Photoisomerization .......................... 463
24.3 [2 + 2] Photodimerization ........................... 465
24.3.1 [2 + 2] Photodimerization of 1,3-Dienes ..... 465
24.3.2 [2 + 2] Photodimerization of Benzyl
Muconates ................................... 465
24.4 Topochemical Polymerization ......................... 469
24.4.1 Features of Topochemical Polymerization ..... 469
24.4.2 Monomer Stacking Structure and
Polymerization Reactivity ................... 470
24.4.3 Shrinking and Expanding Crystals ............ 473
24.4.4 Accumulation and Release of Strain During
Polymerization .............................. 474
24.4.5 Homogeneous and Heterogeneous
Polymerizations ............................. 476
24.5 Conclusion .......................................... 480
References .......................................... 481
25 Reaction Dynamics Studies on Crystalline-State
Photochromism of Rhodium Dithionite Complexes ............. 487
Hidetaka Nakai and Kiyoshi Isobe
25.1 Introduction ........................................ 487
25.2 Photochromism of Rhodium Dithionite Complexes ....... 488
25.3 Reaction Dynamics of Crystalline-State
Photochromism ....................................... 490
25.3.1 Dynamics of Molecular Structural Changes
in Single Crystals .......................... 490
25.3.2 Dynamics of Reaction Cavities in a
Crystalline-State Reaction .................. 495
25.3.3 Dynamics of Surface Morphology Changes of
Photochromic Single Crystals ................ 498
25.4 Summary ............................................. 499
References .......................................... 500
26 Dynamics in Organic Inclusion Crystals of Steroids and
Primary Ammonium Salts .................................... 505
Mikiji Miyata, Norimitsu Tohnai, and Ichiro Hisaki
26.1 Introduction ........................................ 505
26.2 Dynamics of Steroidal Inclusion Crystals ............ 506
26.2.1 Guest-Responsive Molecular Assemblies ....... 506
26.2.2 Intercalation in Steroidal Bilayer
Crystals .................................... 508
26.2.3 Guest Fit Through Weak Non-Covalent Bonds ... 510
26.3 Dynamics of Organic Crystals of Primary Ammonium
Salts ............................................... 512
26.3.1 Solid-State Fluorescence Emission ........... 512
26.3.2 Hydrogen Bond Clusters ...................... 514
26.4 Dynamical Expression of Molecular Information in
Organic Crystals .................................... 516
26.4.1 Hierarchical Structures with
Supramolecular Chirality .................... 516
26.4.2 Expression of Supramolecular Chirality in
Hierarchical Assemblies ..................... 517
26.4.2.1 Three-Axial Chirality ............. 517
26.4.2.2 Tilt Chirality .................... 518
26.4.2.3 Helical and Bundle Chirality in
a 21 Assembly ..................... 519
26.4.3 Supramolecular Chirality of Hydrogen
Bonding Networks ............................ 520
26.4.4 Expression of Molecular Information ......... 522
26.5 Conclusion and Perspectives ......................... 523
References .......................................... 523
27 Morphology Changes of Organic Crystals by Single-
Crystal-to-Single-Crystal Photocyclization ................ 527
Hideko Koshima
27.1 Introduction ........................................ 527
27.2 Surface Morphology Changes in the Salt Crystals
of a Diisopropylbenzophenone Derivative with
Amines via Single-Crystal-to-Single-Crystal
Photocyclization .................................... 528
27.2.1 Solid-State Photocylization ................. 528
27.2.2 Crystal Structures and the Reaction
Mechanism ................................... 529
27.2.3 Morphology Changes in Bulk Crystals ......... 531
27.2.4 Morphology Changes in Microcrystals ......... 532
27.2.5 Correlation between the Morphology Changes
and the Crystal Structural Changes .......... 535
27.3 Morphology Changes in Triisobenzophenone Crystals
via Diastereospecific Single-Crystal-to-Single-
Crystal Photocyclization ............................ 537
27.3.1 Solid-State Photocyclization and the
Crystal Structures .......................... 537
27.3.2 Morphology Changes .......................... 539
27.4 Concluding Remarks .................................. 541
References .......................................... 541
Part Five Single Biocells .................................... 545
28 Femtosecond Laser Tsunami Processing and Light
Scattering Spectroscopic Imaging of Single Animal Cells ... 547
Hiroshi Masuhara, Yoichiroh Hosokawa, Takayuki Uwada,
Guillaume Louit, and Tsuyoshi Asahi
28.1 Introduction ........................................ 547
28.2 Femtosecond Laser Ablation and Generated Impulsive
Force in Water: Laser Tsunami ....................... 548
28.2.1 Manipulation of a Single Polymer Bead by
Laser Tsunami ............................... 551
28.2.2 Manipulation of Single Animal Cells by
Laser Tsunami ............................... 554
28.2.3 Modification and Regeneration Process in
Single Animal Cells by Laser Tsunami ........ 556
28.2.4 Injection of Nanoparticles into Single
Animal Cells by the Laser Tsunami ........... 558
28.3 Development of Rayleigh Light Scattering
Spectroscopy/Imaging System and its Application
to Single Animal Cells .............................. 561
28.4 Summary ............................................. 565
References .......................................... 566
29 Super-Resolution Infrared Microspectroscopy for Single
Cells ..................................................... 571
Makoto Sakai, Keiichi Inoue, and Masaaki Fujii
29.1 Introduction ........................................ 571
29.1.1 Infrared Microscopy ......................... 571
29.1.2 Super-Resolution Microscopy by Two-Color
Double Resonance Spectroscopy ............... 571
29.1.3 Transient Fluorescence Detected IR
Spectroscopy ................................ 572
29.1.4 Application to Super-Resolution Infrared
Microscopy .................................. 573
29.2 Experimental Set-Up for Super-Resolution Infrared
Microscopy .......................................... 574
29.2.1 Picosecond Laser System ..................... 574
29.2.2 Fluorescence Detection System ............... 574
29.2.2.1 Optical Layout for the Solution
and Fluorescent Beads ............. 574
29.2.2.2 Optical Layout for Biological
Samples ........................... 575
29.2.3 Sample ...................................... 576
29.3 Results and Discussion .............................. 576
29.3.1 Transient Fluorescence Image with IR
Super-Resolution in Solution ................ 576
29.3.2 Picosecond Time-Resolved Measurement ........ 578
29.3.3 Application to Fluorescent Beads ............ 579
29.3.4 Application to Whole Cells .................. 581
29.3.4.1 Super-Resolution IR Imaging of
Arabidopsis thaliana Roots ........ 581
29.3.4.2 Vibrational Relaxation Dynamics
in the Cells ...................... 582
29.4 Summary ............................................. 584
References .......................................... 585
30 Three-Dimensional High-Resolution Microspectroscopic
Study of Environment-Sensitive Photosynthetic Membranes ... 589
Shigeichi Kumazaki, Makotoh Hasegawa, Mohammad Ghoneim,
Takahiko Yoshida, Masahide Terazima, Takashi Shiina,
and Isamu Ikegami
30.1 Introduction ........................................ 589
30.1.1 Thylakoid Membranes of Oxygenic
Photosynthesis .............................. 589
30.1.2 Thylakoid Membranes in Chloroplasts ......... 590
30.1.3 Thylakoid Membrane of Cyanobacteria ......... 590
30.1.4 Applications of Fluorescence Microscopy
to a Thylakoid Membrane ..................... 590
30.1.5 Simultaneous Spectral Imaging and its
Merits ...................................... 591
30.2 Spectral Fluorescence Imaging of Thylakoid
Membrane ............................................ 592
30.2.1 Realization of Fast Broadband Spectral
Acquisition in Two-Photon Excitation
Fluorescence Imaging ........................ 592
30.2.2 Spectral Imaging of a Filamentous
Cyanobacterium, Anabaena .................... 594
30.2.2.1 Thylakoid Membrane of
Cyanobacterium .................... 594
30.2.2.2 Stability of the Anabaena
Fluorescence Spectra Under
Photoautotrophic Conditions ....... 594
30.2.2.3 Change of the Anabaena
Fluorescence Spectra by Dark
Some Conditions ................... 595
30.2.2.4 Intracellular Spectral Gradient
in Anabaena Cells ................. 596
30.2.3 Spectral Imaging of Chloroplasts ............ 598
30.2.3.1 Chloroplasts from a Plant, Zea
mays .............................. 598
30.2.3.2 Chloroplast from the Green Alga,
Chlorella ........................ 600
30.3 Technical Verification and Perspective .............. 601
30.4 Summary ............................................. 602
References .......................................... 604
31 Fluorescence Lifetime Imaging Study on Living Cells with
Particular Regard to Electric Field Effects and pH
Dependence ................................................ 607
Nobuhiro Ohta and Takakazu Nakabayashi
31.1 Introduction ........................................ 607
31.2 Experimental ........................................ 608
31.2.1 FLIM Measurement System ..................... 608
31.2.2 Preparation of Hb. salinarum Loaded with
BCECF ....................................... 610
31.2.3 Measurements of External Electric Field
Effects ..................................... 610
31.3 Results and Discussion ................ 611
31.3.1 FLIM of Hb. salinarum ....................... 611
31.3.2 pH Dependence of the Fluorescence Lifetime
in Solution and in Living Cells ............. 614
31.3.3 External Electric Field Effect on
Fluorescence of BCECF ....................... 616
31.3.4 Electric-Field-Induced Aggregate Formation
in Hb. salinarum ............................ 617
31.4 Summary ............................................. 619
References .......................................... 619
32 Multidimensional Fluorescence Imaging for Non-Invasive
Tracking of Cell Responses ................................ 623
Ryosuke Nakamura and Yasuo Kanematsu
32.1 Introduction ........................................ 623
32.2 Materials and Methods ............................... 625
32.2.1 Time-Gated Excitation-Emission Matrix
Spectroscopy ................................ 625
32.2.2 Time- and Spectrally-Resolved Fluorescence
Imaging ..................................... 626
32.2.3 PARAFAC Model ............................... 628
32.2.4 Sample Preparation .......................... 630
32.3 Time-Gated Excitation-Emission Matrix
Spectroscopy ........................................ 630
32.3.1 The 3D Fluorescence Properties of Dye
Solutions ................................... 630
32.3.2 The 3D Fluorescence Property of a Mixed
Solution .................................... 632
32.3.3 PARAFAC Decomposition Without any Prior
Knowledge of Constituents ................... 633
32.4 Time- and Spectrally-Resolved Fluorescence
Imaging ............................................. 635
32.4.1 Characterization of γ-Em Maps ............... 635
32.4.2 Spatial Localization of Fluorescent
Components .................................. 637
32.4.3 PARAFAC Decomposition ....................... 637
32.4.4 Possible Assignments of Fluorescent
Components .................................. 639
32.5 Concluding Remarks .................................. 640
References .......................................... 642
33 Fluorescence Correlation Spectroscopy on Molecular
Diffusion Inside and Outside a Single Living Cell ......... 645
Kiminori Ushida and Masataka Kinjo
33.1 Introduction ........................................ 645
33.1.1 Investigation on Biological System Based
on Molecular Identification and
Visualization ............................... 645
33.1.2 Technical Restrictions and Regulations in
Real-Time Visualization of Material
Transport in Biological System .............. 647
33.1.2.1 Spatial Resolution ................ 647
33.1.2.2 Time Resolution ................... 648
33.1.2.3 Sensitivity ....................... 648
33.1.3 Time and Space Resolution Required to
Observe Anomalous Diffusion of a Single
Molecule in Biological Tissues .............. 648
33.1.4 General Importance of Anomalous Diffusion
in a Signaling Reaction ..................... 652
33.2 Use of Fluorescence Correlation Spectroscopy (FCS)
for Investigation of Biological Systems ............. 655
33.2.1 Use of FCS for Biological Systems ........... 655
33.2.2 Experimental Example of Anomalous
Diffusion Observed in a Model System for
Extracellular Matrices ...................... 656
33.2.3 Quantitative Estimation of Reaction Volume
in Signaling Reaction ....................... 661
33.3 A Short Review of Recent Literature Concerning FCS
Inside and Outside a Single Cell .................... 662
33.3.1 FCS Measurement Inside Single Cells ......... 662
33.3.2 FCS Measurement Outside Cells ............... 664
33.4 Summary ............................................. 664
References .......................................... 665
34 Spectroscopy and Photoreactions of Gold Nanorods in
Living Cells and Organisms ................................ 669
Yasuro Niidome and Takuro Niidome
34.1 Introduction ........................................ 669
34.1.1 Spectroscopic Properties of Gold Nanorods ... 669
34.1.2 Biocompatible Gold Nanorods ................. 670
34.2 Spectroscopy of Gold Nanorods in Living Cells ....... 674
34.2.1 Gold Nanorods Targeting Tumor Cells ......... 674
34.2.2 Spectroscopy of Gold Nanorods In Vivo ....... 675
34.3 Photoreactions of Gold Nanorods for Biochemical
Applications ........................................ 680
34.4 Conclusions and Future Outlook ...................... 682
References .......................................... 683
35 Dynamic Motion of Single Cells and its Relation to
Cellular Properties ....................................... 689
Hideki Matsune, Daisuke Sakurai, Akitomo Hirukawa, Sakae
Takenaka, and Masahiro Kishida
35.1 Introduction ........................................ 689
35.1.1 Single Cell Analysis ........................ 689
35.1.2 Dynamic Motion of Murine Embryonic Stem
Cell ........................................ 690
35.2 Laser Trapping of Biological Cells .................. 691
35.2.1 Optical Tweezers ............................ 691
35.2.2 Set-up for Optical Trapping of a Living
Cell ........................................ 692
35.2.3 Murine Embryonic Stem Cell Trapped with
Optical Tweezers ............................ 693
35.3 Relationship Between Cellular Motion and
Proliferation ....................................... 694
35.3.1 Dynamic Motion of a Murine Embryonic Stem
Cell ........................................ 694
35.3.2 Experimental Procedure ...................... 695
35.4 Cell Separation by Specific Gravity ................. 699
35.4.1 Cell Separation ............................. 699
35.5 Summary ............................................. 700
References .......................................... 701
Index ......................................................... 703
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