LOCAL ELECTRIC FIELD EFFECT ON THE CHLOROPHYLL FLUORESCENCE

Abstract. Polarized absorption and fluorescence of chlorophyll a and bacteriochlorophyll solutions in nematic liquid crystal mixtures have been studied in the presence of an external electric field.
The electric field caused a reorientation of the pigment molecules as concluded from changes in the polarized absorption. However, no correlation was found between the change in the polarized absorption and the change in the polarized fluorescence as a function of the field strength. The field influence was much stronger than expected only from the molecular orientation. The fluorescence polarized parallel to the direction of the liquid crystal was found to increase, whereas the similarly polarized absorption decreases. As a whole, the fluorescence yield significantly increased. It is suggested that the additional electric field is reinforced by a local field, most probably due to a protonation of the liquid crystal molecules.
Charged solvent molecules are reoriented in an external electric field which changes the local electric field acting on chlorophylls. Similar changes in CHI fluorescence yield due to local electric field can be created in vivo by the shift of charged molecules present in surrounding pigments. Such effects can be at least partially responsible for slow induction of fluorescence phenomena.     

The influence of electric field-induced orientation on the retraction of a liquid crystal droplet immersed in a flexible polymer matrix

We measured the apparent interfacial tension between a liquid crystal and a flexible polymer by deformed droplet retraction method. An external electric field is applied to change the director orientation in liquid crystal droplet. The deformation and recovery of a single liquid crystal droplet dispersed in a polydimethylsiloxane (PDMS) matrix were realized by a transient shear flow and observed by polarized optical microscope. In order to control the director orientation in LC droplet, the electric field is applied perpendicular and parallel to the flow field, respectively. The different orientation induced by electric field in liquid crystal droplet has different behavior during droplet retraction and affect the apparent interfacial tension between liquid crystal and flexible polymer.     

Photo-electrochemical control of photosystem II chlorophyll fluorescence in vivo

The effect of electric field on chlorophyll fluorescence is considered on the basis of the reversible radical pair model. The hypothesis is presented that the electric fields generated by photosynthetic charge separation in reaction centers and propagated laterally through the thylakoid lumen are associated with changes in chlorophyll fluorescence yield.     

On the sub-maximal yield and photo-electric stimulation of chlorophyll a fluorescence in single turnover excitations in plant cells

A set of expressions is derived which quantifies the chlorophyll fluorescence yield in terms of rate constants of primary light reactions of PSII, the fraction of open and semi-open RCs and of the electric field sensed by the RC in the thylakoid membrane. The decay kinetics of the chlorophyll fluorescence yield after a single turnover excitation in the presence of DCMU show at least two components, one reversible within approx. 1 s and one with a dark reversion lasting more than 30 s. The latter is attributed to photochemical quenching; the fast component is interpreted to be associated at least partially with photo-electrochemical control. It will be illustrated that (i) the sub-maximal fluorescence yield in single turnover excitation is associated with semi-closure of RCs, (ii) the trapping efficiency of semi-closed centers is less than 50% of that of open centers and (iii) the fluorescence yield of antennas with semi-closed RCs has the highest sensitivity to changes in strength of photo-electric fields.     

Effect of electric field on phase separation of polymer dispersed liquid crystal

The kinetics of the polymerization induced phase separation of liquid crystal (LC)/monomer mixture has been investigated by means of depolarized light intensity technique and polarized light microscope (PLM). To examine the effect of the electric field, a DC electric field was applied across the mixtures during the phase separation process. The kinetic study indicates that the phase separation process is accelerated when the electric field is applied. The morphologies of the formed polymer dispersed liquid crystal (PDLC) films were observed by PLM. The electric field applied during the phase separation process yields the PDLC with small LC domains and fine morphologies. The clearing temperature (T_NI) of the formed PDLC films was measured by the PLM and it is found that the T_NI increases with the applied electric field intensity.     

Polarized infrared study of a polymer network deformation in a nematic liquid crystal host

Using polarized infrared (IR) spectroscopy we have observed deformation of a polymer network in a liquid crystal host during the reorientation of the liquid crystal by an external electric field. In the system studied, containing 2% BMBB-6 polymerized at zero applied field in the host nematic liquid crystal 6CB, the observed deformation angle was between 20^o and 40^o +/- 10^o. These experimental results provide some of the first conclusive experimental evidence that the polymer network elastically deforms as a direct result of the reorientation of the liquid crystal host.     

Permeability control in electro‐sensitive microcapsules with immobilized ferroelectric liquid crystalline segments

Nylon‐polystyrene microcapsules with immobilized ferroelectric liquid crystalline segments were prepared, and permeability control of an encapsulated core material was investigated under an external electric field. A ferroelectric liquid crystal monomer possessing both mesogenicity and chirality responded effectively to the external electrical field. Permeation of the material (oxprenolol) contained in the inner aqueous core of the microcapsules was enhanced under a weak electric field (2 V). Furthermore, the permeability of oxprenolol did not depend on the external electric field in the absence of the ferroelectric liquid crystal segments. To clarify the controlled‐release mechanism of the core material, the light transmittance of the polymer membranes was quantitatively evaluated under an external electric field using a handmade polarized light transmittance apparatus. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1749–1757, 2008     

Polarized infrared study of a polymer network deformation in a nematic liquid crystal host

Using polarized infrared (IR) spectroscopy we have observed deformation of a polymer network in a liquid crystal host during the reorientation of the liquid crystal by an external electric field. In the system studied, containing 2% BMBB-6 polymerized at zero applied field in the host nematic liquid crystal 6CB, the observed deformation angle was between 20^o and 40^o 10^o. These experimental results provide some of the first conclusive experimental evidence that the polymer network elastically deforms as a direct result of the reorientation of the liquid crystal host.     

Tunable polarised fluorescence of quantum dot doped nematic liquid crystals

The concentration, excitation photon wavelength, and polarisation dependent fluorescence of quantum dot (QD)–liquid crystal (LC) mixtures has been studied at room temperature using high-resolution, steady-state fluorescence spectroscopy. The fluorescence of QD–LC mixture increases with increasing QD’s concentration but the spectral red shift of ~10 nm relative to the stock QD–Toluene solution remains independent of concentration. In vertical switching (VS) cells, an external electric field changes the LC alignment direction and enhances the apparent fluorescence intensity. The apparent fluorescence anisotropy compared to that at zero applied electric field monotonically increases up to ~27% at an applied electric field of 0.6 V/µm. These results are consistent with the formation of disc-like assemblages of QDs oriented on planes perpendicular to the director of the nematic liquid crystal (NLC). These findings have important utility in polarisation sensitive photonic devices.     

PICOSECOND FLUORESCENCE KINETICS and ENERGY TRANSFER IN THE ANTENNA CHLOROPHYLLS OF GREEN ALGAE*

Single-photon timing measurements on flowing samples of Chlorella vulgaris and Chlamydomonas reinhardtii at low excitation intensities at room temperature indicate two main kinetic components of the fluorescence at open reaction centers (F₀) of photosystem II with lifetimes of approx. 130 and 500 ps and relative yields of about 30 and 70%. Closing the reaction centers progressively by preincubation of the algae with increasing concentrations of 3-(3′,4′-dichlorophenyl)-l,l-dimethylurea (DCMU) and hydroxylamine gave rise to a slow component with a lifetime increasing from 1.4 to 2.2 ns (F_max) The yield of the slow component increased to 65-68% of the total fluorescence yield in parallel to a decrease in the yield of the fast component to a value close to zero at the f_max-level. The 130 ps lifetime of the fast component remained unchanged. The middle component showed an increase of its lifetime from 500 to 1100 ps and of its yield by a factor of 1.5. Spacing of the ps laser pulses by 12 μs allowed us to resolve a new long-lived fluorescence component of very small amplitude which is ascribed to a small amount of chlorophyll not connected to functional antennae. The opposite dependence of the yield of the fast and the slow component on the state of the reaction centers at almost constant lifetimes is consistent with a mechanism of energy conversion in largely separately functioning photosystem II units. Yields and lifetimes of these two components are in agreement with the high quantum yield of photosynthesis. The lower lifetime limit of 1.4 ns of the slow component is assigned to the average transfer time of an excited state from a closed to a neighboring open reaction center and the increase in the lifetime to 2.2 ns is evidence for a limited energy transfer between photosystems II. Relative effects of changing the excitation wavelength from 630 to 652 nm on the relative fluorescence yields of the kinetic components were studied at the fluorescence wavelengths 682, 703 and 730 nm. Our data indicate that (i) the middle component has its fluorescence maximum at shorter wavelength than the fast component and (ii) that the antennae chlorophylls giving rise to the middle component are preferentially excited by 652 nm light. It is concluded that the middle component originates from the light-harvesting chlorophyll alb protein complexes and the major portion of the fast component from the chlorophyll a antennae of open photosystem II reaction centers.     

电场对聚肽液晶相行为的影响

聚合物液晶的相转变不仅可以通过溶液温度或聚合物的浓度的改变来实现,也可以通过施加外电场、磁场等取向场来达到．在二氧六环、氯仿、间甲酚等支持聚肽a一螺旋构象的溶剂中,当PBLG(聚L-谷氨酸γ-苯甲酯)达到一定的浓度会形成胆甾型溶致液晶．对这种液晶施加强度足够     

酞菁聚合物薄膜的电场取向和光导性能研究

通过电场取向法成功地制备了酞菁类聚合物(PPc)有序薄膜,并采用偏振荧光和TEM技术对其取向进行了研究.分别以该PPC有序薄膜和腙类作为载流子发生层和载流子传输层制备光电导体,发现其光导性能优于不加电场制备的PPc薄膜,呈现了光导性能提高的材料结构低维化效应.     

Linear and non-linear liquid crystal materials, electro-optical effects and surface interactions. Their application in present and future devices

The structural, material and electro-optical properties of novel, halogenated nematic liquid crystals which contain quite different functional groups are correlated. Synergisms which lead to broad mesophases, low viscosities and large dielectric anisotropies further improve the performance of actively and passively addressed, high information content liquid crystal displays. Some recent developments, such as operation of supertwisted nematic displays with not only linear, but also circularly polarized light, are included. A recently presented, efficient liquid crystal colour projection concept, whose functional elements, i.e. polarizers, filters and modulators, consist entirely of liquid crystal devices, is reviewed. Its circular polarizers and filters are made up of novel, negative dielectric anisotropic cholesteric liquid crystals designed such that, dislocation-free, optically uniform, planar textures result from electric field alignment. Novel, non-linear optical ferroelectric liquid crystals which exhibit very large and stable second order harmonic coefficients d₂₂ = 5 pm V^-1 have the potential to be used in integrated optical devices, such as frequency converters and Pockels modulators. Photopolymerization of polymer-coated substrates with linearly polarized light is shown to induce anisotropic, uniaxial orientation of the polymer side chains without mechanical treatment. The resulting anisotropic dispersive surface interaction forces align adjacent liquid crystal molecules parallel. This new, photoinduced liquid crystal aligning technique renders the generation of azimuthal director patterns possible. It opens up interesting possibilities for realizing new optical and electro-optical devices, including hybrid and stereo liquid crystal displays.     

PHOTOCHEMICAL AND SPECTRAL PROPERTIES OF A PARTICULATE MODEL SYSTEM OF CHLOROPHYLL WITH AMPHIPHILES PREPARED FROM HISTAMINE

Abstract— In the photosynthesis model system described, chlorophyll a at an interface photosensitizes the transfer of hydrogen equivalents from a hydrocarbon phase to an aqueous phase. The hydrocarbon phase, to which chlorophyll is adsorbed, consists of polyethylene particles swollen with tetradecane. The particles are also charged positive by co-adsorption of dodecylpyridinium iodide. Furthermore, chlorophyll is ligated with the imidazole function of one of several amphiphiles derived from histamine, which may or may not contain a reducible nitroaromatic group that can serve as primary electron acceptor from photoexcited chlorophyll. The fluorescence quantum yield of chlorophyll on these particles is diminished by self-association of the pigment and by reaction with an oxidizing amphiphile; in the latter case, the quantum yield is correlated with the one-electron redox potential of the amphiphile. Fluorescence-lifetime analysis reveals that most excited singlet states of chlorophyll are quenched rather quickly, and that most of the fluorescence comes from a small fraction of chlorophyll with long lifetime. All preparations sensitize the photoreduction of 5,5′-dithiobis(2-nitrobenzoate) (DTNB) to the water-soluble thiolate by hydrazobenzene. When the amphiphile that ligates chlorophyll is not oxidizing, the quantum yield of photoreduction is unrelated to the fluorescence yield of the particles, but may be related to the degree of self-association of chlorophyll. When the amphiphile that ligates chlorophyll is oxidizing, the kinetics of photoreduction of DTNB require that the electron passes through the primary oxidant to DTNB. Quantum yields for photosensitized reducton of oxidizing amphiphiles in the absence of DTNB have a reversed correlation with redox potential, which can be rationalized in terms of the Marcus theory of electron transfer. All data are most consistently accounted for if the primary photoproduct is an ion pair of chlorophyll and primary oxidant when the latter is available, and a chlorophyll radical ion pair when it is not, both formed by electron transfer from the singlet excited state of chlorophyll.     

Reorientation behaviour of bent core molecules in response to an external electric field as detected by time-resolved FTIR spectroscopy

Time-resolved polarized Fourier transform infrared spectroscopy (FTIR) is employed to analyse the segmental orientation and mobility of achiral bent core molecules in response to an external electric field. By shearing the substance between ITO coated CaF2 windows two types of domain, racemic and homochiral, are formed in the high temperature B2 phase. Each of these domains is characterized by two spontaneous symmetry-breaking instabilities which yield a symmetric and an antisymmetric electro-optical response, respectively. Taking advantage of the specificity of IR spectroscopy, this switching behaviour is analysed on a molecular level for the moieties of the bent core liquid crystal materials. In this way, the electrically induced reorientation of the different segments on a cone and the suppression of the antiferroelectric structure at higher frequencies can be followed in detail. Furthermore the biased rotation of the two carbonyl groups around the molecular long axis is determined. It is shown that all molecular units move synchronously on the time scale of the experiment (10mus).     

Reorientation behaviour of bent core molecules in response to an external electric field as detected by time-resolved FTIR spectroscopy

Time-resolved polarized Fourier transform infrared spectroscopy (FTIR) is employed to analyse the segmental orientation and mobility of achiral bent core molecules in response to an external electric field. By shearing the substance between ITO coated CaF2 windows two types of domain, racemic and homochiral, are formed in the high temperature B2 phase. Each of these domains is characterized by two spontaneous symmetry-breaking instabilities which yield a symmetric and an antisymmetric electro-optical response, respectively. Taking advantage of the specificity of IR spectroscopy, this switching behaviour is analysed on a molecular level for the moieties of the bent core liquid crystal materials. In this way, the electrically induced reorientation of the different segments on a cone and the suppression of the antiferroelectric structure at higher frequencies can be followed in detail. Furthermore the biased rotation of the two carbonyl groups around the molecular long axis is determined. It is shown that all molecular units move synchronously on the time scale of the experiment (10mus).     

Relaxation of a liquid-crystalline order induced by an electric field

The influence of a strong electric field on isotropic melts of 6-cyanobiphenyl and comb-shaped polyacrylate with mesogenic groups in its side chains is investigated. It is established that the electric field induces the isotropic liquid-nematic liquid crystal phase transition in melts of these compounds. A relaxation process was discovered that destroys the nematic ordering induced in substances by electric fields. It was established that, for polymer liquid crystals, the time of transition from the ordered state to the isotropic phase is several orders longer then that for low-molecular liquid crystal.     

High-contrast electrically switchable light-emitting liquid crystal displays based on α-cyanostilbenic derivative

Light-emitting liquid crystal displays (LE-LCDs), serving as emissive displays, are considered as promising alternatives to conventional LCDs because of their superior power efficiency. A dichroic fluorescent dye (Z)-2-(4-aminophenyl)-3-(4-(fluorophenyl)acrylonitrile (CN-AFAN) is synthesised, which exhibits strong fluorescence in the solution and solid states. Moreover, an electrically switchable optical switch based on CN-AFAN and a cholesteric liquid crystal is demonstrated, which combines the internal scattering of excitation light and the dichroism of CN-AFAN to improve fluorescence contrast. The photoluminescence and transmittance of the optical switch is modulated by an electric field between the planar state, focal conic state, and homeotropic state. The resultant device is cost-effective and easy to fabricate, thereby demonstrating immense potential for security and display applications.     

Electrically induced and thermally erased properties of side‐chain liquid crystalline polymer/liquid crystal/chiral dopant composites

The properties of synthesized side‐chain liquid crystalline polymer (SCLCP)/liquid crystal (LC)/chiral dopant composites having a chiral nematic (N*) phase at room temperature were investigated by polarized optical microscopy (POM) and a UV/VIS/NIR spectrophotometer. The composite exhibited a planar texture after it was filled into cells under homogeneous boundary conditions and it was transparent. When an electric field was applied to the composite, a focal conic texture was formed and the composite became light scattering. After the electric field was turned off, the light‐scattering state remained stable for some time, i.e. the light‐scattering state exhibited a memory effect. The focal conic texture changed into the planar texture when the composite was heated and the composite became transparent again. Therefore, the composite had electrically induced and thermally erased properties. The SCLCP had some influence on the memory effect and on the thermo‐electro‐optical properties of the composite.     

Electrically induced and thermally erased properties of side-chain liquid crystalline polymer/liquid crystal/chiral dopant composites

The properties of synthesized side-chain liquid crystalline polymer (SCLCP)/liquid crystal (LC)/chiral dopant composites having a chiral nematic (N*) phase at room temperature were investigated by polarized optical microscopy (POM) and a UV/VIS/NIR spectrophotometer. The composite exhibited a planar texture after it was filled into cells under homogeneous boundary conditions and it was transparent. When an electric field was applied to the composite, a focal conic texture was formed and the composite became light scattering. After the electric field was turned off, the light-scattering state remained stable for some time, i.e. the light-scattering state exhibited a memory effect. The focal conic texture changed into the planar texture when the composite was heated and the composite became transparent again. Therefore, the composite had electrically induced and thermally erased properties. The SCLCP had some influence on the memory effect and on the thermo-electro-optical properties of the composite.