Time-resolved synchrotron X-ray study of crystalline phase transition in poly(aryl ether ketone ketone) containing alternated terephthalic/isophthalic moieties

Unique crystallization and melting behavior in poly(aryl ether ketone ketone) containing alternated terephthalic and isophthalic moieties were studied by time-resolved synchrotron x-ray methods. Recently, this material has been shown to exhibit three polymorphs (forms I, II, and III). In this work, we further investigated their distinctive thermal properties and found that form I is the dominating and the most thermally stable phase while form II is favored by fast nucleation conditions and is the least stable phase. On the other hand, form III represents a minor intermediate phase that usually coexists with form I and can be transferred from form II and to form I. Structural and morphological changes in form I have been followed by simultaneous wide-angle x-ray diffraction (WAXD)/small-angle x-ray scattering (SAXS) measurements during cold- or melt-crystallization and subsequent melting. In all cases, a larger dimensional change was found in the crystallographic a-axis than the b-axis during heating and cooling. This may be due to the greater lateral stress variation with respect to temperature along the a direction of the primary lamellae which is induced by either the formation of secondary lamellae or the preferential chain-folding direction in poly(aryl ether ketone ketone)s. During the phase transitions of form II ← III in the cold-crystallized specimen and form III ← I in the melt-crystallized samples, lamellar variables (long period, lamellar thickness, and invariant) obtained from SAXS remain almost constant. This indicates that the density distribution in the long spacing is independent of the melting in form II or III. For melt-crystallization, the corresponding changes in unit-cell dimensions and lamellar morphology during the annealing-induced low endotherm are most consistent with the argument that these changes are due to the melting of thin lamellar population. © 1995 John Wiley & Sons, Inc.     

Time-resolved fluorescence study of the single tryptophan in thiocyanate and azide derivatives of horseradish peroxidase: Implication for a p H-induced conformational change in the heme cavity

Detailed pH-dependent steady state and picosecond time-resolved tryptophan fluorescence studies on thiocyanate and azide complexes of horseradish peroxidase have been carried out. The fluorescence decay of the single tryptophan in these species was fitted to a discrete three exponential model. Maximum entropy method analysis also gave three distinct regions of lifetime distributions. The fast subnanosecond lifetime component was found to have > 97% amplitude contribution while other two longer lifetime components have small contributions. Small contributions from the nanosecond lifetime components possibly arise from apoprotein impurity or some small amount of disordered heme conformer of the protein. pH dependence of the fast picosecond lifetime components was found to show a systematic behavior which has been interpreted in the light of obligatory conformation change associated with activation of the enzyme at low pH.     

Anomalies in the Absorption and Reflection of a High-Power Ultrashort Laser Pulse by a Plasma with a Solid-State Density

The patterns of absorption and reflection of an ultrashort laser pulse by a plasma with a solid-state density, which are realized in the mode of the normal skin effect, are studied. It is shown that a decrease in low-power pulse duration shorter than the period corresponding to the fundamental frequency of radiation leads to an increase in the absorption coefficient. If the pulse power is so high as to provide electron heating during a time shorter than the reciprocal fundamental frequency, nonlinear suppression of absorption takes place and the spectrum of the reflected radiation contains odd harmonics of the fundamental frequency.     

Structure induced by irradiation of femtosecond laser pulse in dyed polymeric materials

We investigated the structures induced by an irradiation of a near‐infrared (NIR) femtosecond laser pulse in dye‐doped polymeric materials {poly(methyl methacrylate) (PMMA), thermoplastic epoxy resin (Epoxy), and a block copolymer of methyl methacrylate and ethyl acrylate‐butyl acrylate [p(MMA/EA‐BA) block copolymer]}. Dyes used were classified into two types—type 1 with absorption at 400 nm and type 2 with no absorption at 400 nm. The 400‐nm wavelength corresponds to the two‐photon absorption region by the irradiated NIR laser pulse at 800 nm. Type 1 dye‐doped PMMA and p(MMA/EA‐BA) block copolymer showed a peculiar dye additive effect for the structures induced by the line irradiation of a NIR femtosecond laser pulse. On the contrary, dye‐doped Epoxy did not exhibit a dye additive effect. The different results among PMMA, p(MMA/EA‐BA) block copolymer, and Epoxy matrix polymers are supposed to be related to the difference of electron‐acceptor properties. The mechanism of this type 1 dye‐additive‐effect phenomenon for PMMA and p(MMA/EA‐BA) block copolymer is discussed on the basis of two‐photon absorption of type 1 dye at 400 nm by the irradiation of a femtosecond laser pulse with 800 nm wavelength and the dissipation of the absorbed energy to the polymer matrix among various transition processes. Dyes with a low‐fluorescence quantum yield favored the formation of thicker grating structures. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2800–2806, 2002     

Picosecond dynamics of intramolecular charge transfer in benzophenone amino derivatives

Institute of Molecular and Atomic Physics, Academy of Sciences of Belarus, 70 F. Skaryna Ave, Minsk 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 62, No. 3, pp. 49–55, May–June, 1995.     

Transient Spectroscopic Properties of [60] Fullerene—Containing Cyclic Sulphoxide

The properties of the triplet excited state of [60] fullerene-containing cyclic sulphoxide have been investigated by time-resolved absorption spectroscopy. Transient absorption bands of [60] fullerene-containing cyclic sulphoxide showed two decay-components, which wrer attributed to triplet excited states of different spin multiplicity. The properties of photoexcited states of [60] fullerene-containing cyclic sulphoxide are also reported.     

Dynamics of excited m-dichlorobenzene

Dichlorobenzene is a precursor molecule of di-oxins, which are some of the most toxic chemicals and are suspected of being mutagenic with the structure of benzene rings containing different numbers of chlorine atoms. They are seriously harmful to the health of human. Therefore, it is necessary to study these aryl chemicals especially dichlorobenzene molecules in great detail. In recent years, a number of groups have investi-gated the molecules of aryl halide. The near ultraviolet absorption sp…     

飞秒激光在6H-SiC表面诱导偏振依赖纳米结构特性研究

激光诱导偏振依赖纳米结构是一种有效实现纳米图案化的技术,并且一直备受研究者的青睐。利用飞秒激光微加工技术,对6H-SiC晶体表面激光诱导偏振依赖纳米结构特性进行了研究。通过改变入射激光加工偏振态和延迟时间样品表面诱导产生了直径约为150 nm的球形纳米颗粒、椭圆形纳米颗粒和空间周期约为150 nm的高空间频率表面条纹结构。实验结果表明,入射激光偏振特性会直接影响诱导产生的微结构形貌,并且优先入射的飞秒激光对最终产生的表面微结构形貌有决定性作用。初步探讨了偏振依赖纳米结构形成的物理机制,表面等离激元(surface plasmon polariton, SPP)在表面微纳米结构的产生过程中扮演着重要角色,研究结果对激光诱导表面周期结构(laser-induced periodic surface structures, LIPSS)可控制备具有重要意义。     

Femtosecond Laser 4D Printing of Light-Driven Intelligent Micromachines

Intelligent micromachines that respond to external light stimuli have a broad range of potential applications, such as microbots, biomedicine, and adaptive optics. However, artificial light-driven intelligent micromachines with a low actuation threshold, rapid responsiveness, and designable and precise 3D transformation capability remain unachievable to date. Here, a single-material and one-step 4D printing strategy are proposed to enable the nanomanufacturing of agile and low-threshold light-driven 3D micromachines with programmable shape-morphing characteristics. The as-developed carbon nanotube-doped composite hydrogel simultaneously enhanced the light absorption, thermal conductivity, and mechanical modulus of the crosslinked network, thus significantly increasing the light sensitivity and response speed of micromachines. Moreover, the structural design and assembly of asymmetric microscale mechanical metamaterial unit cells enable the highly efficient additive nanomanufacturing of 3D shape-morphable micromachines with large dynamic modulation and spatiotemporal controllability. Using this strategy, the world's smallest artificial beating heart with programmable light-stimulus responsiveness for the cardiac cycle is successfully printed. This 4D printing method paves the way for the construction of multifunctional intelligent micromachines for bionics, drug delivery, integrated microsystems, and other fields.