Conformation and transport properties of poly(alkylene phosphate)—A synthetic analogue of natural teichoic acids—I. Hypercoiled to extended coil state transition in poly(1,3-propylene phosphate)

The pH-induced conformational transition of poly(1,3-propylene phosphate) (PPP) in an aqueous solution has been investigated by the potentiometric method. It has been found that PPP undergoes a cooperative macroconformational transition upon changing the fraction of dissociated phosphate groups from 0.3 to 0.4. The standard free energy for the transition from a hypothetical hypercoiled form to a loosely coiled form was estimated to be 565 J/mol.     

Continuous and discontinuous phase transitions in ammonium halides

Raman spectra of NH₄Cl and NH₄Br have been recorded as functions of temperature and pressure. The λ-type phase transition in NH₄Cl has been studied as (i) a weakly first order. (ii) a tricritical and (iii) a second order transition. A strongly first order transition has been studied in NH₄Br. The analysis of the data has concentrated on the correlation of frequency shift with volume change across the phase change regions. This correlation has been established for the frequencies of the ν₂ and ν₅ Raman modes of NH₄Cl at zero pressure (1st order) 1.6 kbar (tricritical) and 2.8 kbar (2nd order), and the frequencies of the ν₅ Raman mode of NH₄Br at zero pressure (1st order). A single Y (mode Grünelsen parameter) has been shown to describe each frequency shift right through the phase change region once an order-disorder contribution has been introduced at and below the transition temperatures.     

聚对偶氮氧苯酚酯系列热致性液晶高分子的相转变

合成含有不同亚甲基数（ｎ＝４—１２，１４）的主链型热致性液晶高分子──聚对偶氮氧苯酚二元羧酸酯．用ＤＳＣ和ＦＴＩＲ观测了相转变的奇偶效应，揭示了液晶相转变过程中分子间相互作用力性质的变化．并与聚２，２＇－二甲基对偶氮氧苯酚二元羧酸酯系列进行了比较，讨论了中介单元的对称性对液晶高聚物相转变和对液晶相稳定性的影响．     

Critical behaviour of a polar-polar binary system from optical birefringence measurements

High resolution measurements of optical birefringence (Δn) have been carried out to study the critical behaviour at the nematic-isotropic (N–I) and smectic A-nematic (SmA–N) phase transitions in a binary system composed of nonyloxycyanobiphenyl (9OCB) and heptylcyanobiphenyl (7CB). From a fitting procedure compatible with the weakly first order nature of the N–I transition, the order parameter critical exponent β at the N–I transition has been found to be in well agreement with the tricritical hypothesis. The pretransitional behaviour at the SmA–N transition has been investigated with the aid of a differential parameter extracted from Δn data and the yielded critical exponent α has been found to be non-universal in nature. A weak birefringence have been found to develop on approaching the N–I transition temperature, which is tentatively attributed to surface induced ordering. In this case, a treatment identical to that for the SmA–N transition yields a tricritical nature for the N–I transition in the investigated mixtures. Such an outcome has also appeared to be in well agreement with those obtained from the direct analysis of the Δn data (i.e. in parameterisation of β).     

Imaging new transient nanostructures using a microfluidic chip integrated with a controlled environment vitrification system for cryogenic transmission electron microscopy

Nanostructures (vesicles, micelles, bilayers) are important in nanomedicine and biochemical processes. They are agents for encapsulation and eventual release of drugs, flavors, and fragrances. The structural transition from micelles to vesicles through disk-like intermediate states has been demonstrated previously. Here, we disclose a new route for the micelle-vesicle transition, where micelles aggregate to first form long tubules that become unstable, and break up into vesicles. A simple theory, based on energy principles, is presented to explain the tubule-vesicle transition. Observation of this new tubular intermediate state has been facilitated by the development of an integrated microfluidic chip/cryogenic transmission electron microscopy (cryo-TEM) unit. Although this transition has been observed in a specific amphiphilic system where micellar solutions of cetyltrimethylammonium bromide (CTAB) and dodecylbenzene sulfonic acid (HDBS) are mixed to form vesicles, this new tool can be applied broadly to study transient structures in nanoscale systems under the very controlled conditions provided by microfluidics.     

Biodegradable PEO/cellulose‐based solid–solid phase change materials

A series of poly(ethylene oxide) (PEO) blends with cellulose (CEL) or cellulose derivatives—carboxymethyl cellulose (CMC), cellulose acetate (CAC), and cellulose ether (CET)—has been investigated as phase change materials for thermal energy storage. For PEO/CEL blends solid–solid phase transition has been observed in the whole concentration's range; for PEO/CMC and PEO/CET blends solid–solid phase transition has been found for PEO content 25 or 50 and 25 wt%, respectively. Otherwise, solid–liquid phase transition takes place. MTDSC investigations revealed that for PEO/CEL and PEO/CMC blends transition the strongest recrystallization effect (as evidenced by exothermic effect in reversing heat flow) as melting process occurred. FTIR analysis shows a shift of the stretching vibration bands of both the proton‐donor O? H groups from CEL and PEO due to intermolecular hydrogen interactions between the blends' components. Copyright © 2010 John Wiley & Sons, Ltd.     

Separation of transition metal ions and preconcentration of platinum (IV) and chromium (III) on alumina-immobilized diethylenetriaminepentaacetic acid by ligand exchange

Summary Basic alumina-bonded diethylenetriaminepentaacetic acid (DTPA) has been utilized for the separation and preconcentration of some transition metal ions on the basis of ligand exchange. Breakthrough capacity and rate of sorption have been studied. The distribution coefficients of 16 transition metal ions have been determined in demineralized water, 0.01 M sodium citrate and in four different pH systems. On the basis of differences in Kd values some quantitative separations of metal ions have been achieved. The greater selectivity behaviour (higher Kd values) of the adsorbent for Pt(IV)and Cr(III) has been utilized for their preconcentration in the presence of other metal ions. The method has been employed for the recovery of Pt(IV) and Cr(III) from tapwater and sea-water samples.     

Molecular organization of the lipid-bound EDTA—chromium(III) complex

Ethylenediaminetetraacetic acid bound to a lipid (dioctadecyldimethylammonium bromide) has been used as an immobilized ligand system for extracting chromium(III) salts from an aqueous solution. The morphology and nature of the aggregation of the metal-ion-bound lipid—ligand complex has been studied by transmission electron microscopy and differential scanning calorimetry. A strong dependence of the vesicle size on the gel—crystalline phase transition has been observed and the results are rationalized in terms of higher-ordered packing of the large vesicles below the phase transition temperatures.     

硅杂环丙烯异构化反应的理论研究

用量子化学理论方法研究了硅杂环丙烯单重态的异构化反应。结果表明:该异构化反应的过渡态为三元环结构,该反应为氢迁移反应;反应的势垒高度为276.67kJ·mol^-^1[MP2/6-31G(d)]。通过内禀反应坐标(IRC)计算,获得了沿反应途径的势能剖面。     

Polarization of the excimer-type transition in 9-anthroic acid

The polarization of an excimer-type transition in 9-anthroic acid (9-anthracenecarboxylic acid) has been determined experimentally. A negative polarization of the excimer-type transition was observed with respect to the in-plane excitation. The polarization of the excimer-type transition has a component perpendicular to the molecular plane.     

Charge and salt-driven reentrant order-disorder and gas-solid transitions in charged colloids

Monte Carlo simulations have been performed for aqueous charged colloidal suspensions as a function of effective charge density (sigma) on the particles and salt concentration C(s). We vary the effective charge density in our simulations over a range where a reentrant solid-liquid transition in suspensions of silica and polymer latex particles has been reported by Yamanaka et al. (Phys. Rev. Lett. 80 (1998) 5806). We show that at low ionic strengths a homogeneous liquid-like ordered suspension undergoes crystallization upon increasing sigma. Further increase in sigma resulted once again in a disordered state, which is in agreement with experimental observations. In addition to this reentrant order-disorder transition, we observe an inhomogeneous-to-homogeneous transition in our simulations when salt is added to the disordered inhomogeneous state. This inhomogeneous-to-homogeneous disordered transition is analogous to the solid-gas transition of atomic systems and has not yet been observed in charged colloids. The reported experimental observations on charged colloidal suspensions are discussed in the light of present simulation results.     

Thermoanalytical and Spectroscopic Characterization of Solid State Dipyridamole

A physico-chemical characterization of dipyridamole (C₂₄H₄₀N₈O₄), a widely used anti-aggregating agent, has been performed by using a combination of thermoanalytical (DSC) and spectroscopic (XRPD and FT-IR/PAS) techniques. A solid state transition, already reported in literature, has been ascribed to the breaking of an intramolecular H-bonds network. The rupture of a network of intermolecular H-bonds is thought to accompany the fusion. The solid state transition has been shown to be reversible provided the sample has not undergone melting. Mechanical milling and thermal annealing have been shown to decrease melting temperature and enthalpy. The effect brought about by mechanical and thermal treatment on the solid state transition is different. In the milled samples the transition peak shifts towards lower temperatures and its enthalpy suggests that all intramolecular H-bonds have been transformed into intermolecular H-bonds. This revised version was published online in August 2006 with corrections to the Cover Date.     

On the excited state dynamics of vibronic transitions. High-resolution electronic spectra of acenaphthene and its argon van der Waals complex in the gas phase

Rotationally resolved fluorescence excitation spectroscopy has been used to study the dynamics, electronic distribution, and the relative orientation of the transition moment vector in several vibronic transitions of acenaphthene (ACN) and in its Ar van der Waals (vdW) complex. The 0(0)(0) band of the S(1) ← S(0) transition of ACN exhibits a transition moment orientation parallel to its a-inertial axis. However, some of the vibronic bands exhibit a transition moment orientation parallel to the b-inertial axis, suggesting a Herzberg-Teller coupling with the S(2) state. Additionally, some other vibronic bands exhibit anomalous intensity patterns in several of their rotational transitions. A Fermi resonance involving two near degenerate vibrations has been proposed to explain this behavior. The high-resolution electronic spectrum of the ACN-Ar vdW complex has also been obtained and fully analyzed. The results indicate that the weakly attached argon atom is located on top of the plane of the bare molecule at ~3.48 ? away from its center of mass in the S(0) electronic state.     

Electroclinic effect near a smectic A-chiral smectic I transition

The electroclinic effect in the S_A phase of (S) (4'-decyloxy-2'-hydroxybenzylidene)-4-amino(1-ethoxycarbonylethyl) cinnamate has been studied. The induced tilt angles have been measured as a function of temperature near the S_A-S*_I transition at 87°C. The response of the material to different voltages and frequencies has been analysed by using two complementary optical techniques. At low A.C. probe fields the amplitude of the induced tilt shows a relaxational behaviour which can be described by a single relaxation time. The relaxation frequencies have been found to be linear in temperature near the transition, in a similar way to the S_A-S*_C transition.     

Investigation of conformational transition in poly(cyclohexyl methacrylate)

The variations of intrinsic viscosity and refractive index increment with temperature for poly(cyclohexyl methacrylate) in isobutyl methyl ketone have been studied. A conformational transition has been found in the range 10–30°C. The influence of the molar volume of the side-group on the conformational transition temperature has also been discussed with respect to results for related polymers.     

Revert and direct type Liesegang phenomenon of silver iodide

The experimental conditions for Liesegang phenomenon of silver iodide in agar gel columns, and particularly the transition from revert to direct type of periodic precipitations, have been investigated. The theoretically derived Mathur's spacing law, which suits both revert and direct type of Liesegang's rings, has been experimentally verified. An attempt has been made to explain the mechanism of revert and direct type and of the transition of revert to direct type of periodic precipitation on the basis of adsorption on the precipitated silver iodide and of flocculation. The dependence of the transition point on the concentrations of the outer and inner electrolytes has been studied. The time law of Morse and Pierce has been verified. The dependence of the velocity constant ( ) on the concentrations of the outer and inner electrolytes has been studied.     

Unusual spin-transition anomaly in the crossover system [Fe(2-pic)3]Cl2·EtOH

The spin transition in [Fe(2-pic)₃]Cl₂·EtOH (2-pic = 2-picolylamine) has been reinvestigated by Mössbauer spectroscopy and magnetic susceptibility measurements. With both techniques we see a “two-step” spin conversion in the crossover region with transition temperatures at 120.7 and 114.0 K. This has never been reported for any other spin crossover system. The quadrupole splittings for both spin states change abruptly in the range of the transition.     

几种热塑性特种工程塑料的热分析研究

聚芳醚和聚芳硫醚两类聚合物都为热塑性的耐高温特种高分子材料 ,由于它们的加工性好、加工成型效率高 ,受到了世界各国的高度重视。这两类聚合物在结构上有许多相似之处 ,如它们的主链都含苯环、酮基或砜基 ,而聚芳醚类聚合物的柔性基团为醚键 ,聚芳硫醚类聚合物的柔性基团为硫醚键 ,但由于氧和硫在元素周期表中属于同一族元素 ,原子结构仍然相似 ,因而在某些方面具有一定的可比性。研究它们的性能差异对于改进聚合物性能以及进行进一步的结构设计将有一定的帮助。在这两类聚合物中 ,国内已商品化生产的品种有ＰＥＥＫ、ＰＥＳ和ＰＰＳ ,有…     

Microdetermination of the degree of hydration of polysaccharides and glycoproteins

In the hydration of polysaccharides and glycoproteins a "glass transition effect" has been discovered, i.e., a phase transition, at certain critical values of the relative water-vapour pressure (P/P(s))(gt), of lyophilized preparations to a new state which is accompanied by a "glass transition" of the samples. The dependence of (P/P(s))(gt) the content of polysaccharide and glycoprotein has been shown. Conditions have been found which make it possible to measure the absolute value of the degree of hydration of such biopolymers at any values of p/p(s), by means of Karl Fischer titration.     

In-situ TEM investigation of MoS_2 upon alkali metal intercalation

Phase transition in two dimensional molybdenum disulfide (MoS_2) can be induced by several methods and has been investigated for decades. Alkali metal insertion of MoS_2 had been proved an effective method to cause phase transition early in 1970s, and has been gaining renewed interest recently, due to the possible application of MoS_2 in energy storage. The alkali metal intercalation of MoS_2 has been studied by various techniques, among which in-situ transmission electron microscopy (TEM) provides unique capability of real time resolving the structural evolution of the materials at high spatial resolutions. Here by in-situ TEM technique we investigated the structural evolution of MoS_2 upon lithium and sodium intercalation, along with transformation of the nanosheet and variation of the electron diffraction patterns. The intercalation process is accompanied by emergence of superstructures, which exist in several forms. The ion intercalation results in phase transition of MoS_2 from 2H to 1T, and the driving mechanism of the phase transition are discussed. The work provides a more comprehensive understanding of ion intercalation induced phase transition of MoS_2.