Rational Design, Multistep Synthesis and in Vitro Evaluation of Poly(glycerol) Functionalized Nanodiamond Conjugated with Boron-10 Cluster and Active Targeting Moiety for Boron Neutron Capture Therapy.

Boron neutron capture therapy (BNCT), advanced cancer treatment utilizing nuclear fission of ¹⁰ B atom in cancer cells, is attracting increasing attention. As ¹⁰ B delivery agent, sodium borocaptate (¹⁰ BSH, ¹⁰ B₁₂ H₁₁ SH ⋅ 2Na), has been used in clinical studies along with L-boronophenylalanine. Recently, this boron cluster has been conjugated with lipids, polymers or nanoparticles to increase selectivity to and retentivity in tumor. In this work, anticancer nanoformulations for BNCT are designed, consisting of poly(glycerol) functionalized detonation nanodiamonds (DND-PG) as a hydrophilic nanocarrier, the boron cluster moiety (¹⁰ B₁₂ H₁₁ ^2- ) as a dense boron-10 source, and phenylboronic acid or RGD peptide as an active targeting moiety. Some hydroxy groups in PG were oxidized to carboxy groups (DND-PG-COOH) to conjugate the active targeting moiety. Some hydroxy groups in DND-PG-COOH were then transformed to azide to conjugate ¹⁰ B₁₂ H₁₁ ^2- through click chemistry. The nanodrugs were evaluated in vitro using B16 murine melanoma cells in terms of cell viability, BNCT efficacy and cellular uptake. As a result, the ¹⁰ B₁₂ H₁₁ ^2- moiety is found to facilitate cellular uptake probably due to its negative charge. Upon thermal neutron irradiation, the nanodrugs with ¹⁰ B₁₂ H₁₁ ^2- moiety exhibited good anticancer efficacies with slight differences with and without targeting moiety.

Rational Design, Multistep Synthesis and in Vitro Evaluation of Poly(glycerol) Functionalized Nanodiamond Conjugated with Boron-10 Cluster and Active Targeting Moiety for Boron Neutron Capture Therapy.

Boron neutron capture therapy (BNCT), advanced cancer treatment utilizing nuclear fission of 10 B atom in cancer cells, is attracting increasing attention. As 10 B delivery agent, sodium borocaptate (10 BSH, 10 B12 H11 SH ⋅ 2Na), has been used in clinical studies along with L-boronophenylalanine. Recently, this boron cluster has been conjugated with lipids, polymers or nanoparticles to increase selectivity to and retentivity in tumor. In this work, anticancer nanoformulations for BNCT are designed, consisting of poly(glycerol) functionalized detonation nanodiamonds (DND-PG) as a hydrophilic nanocarrier, the boron cluster moiety (10 B12 H11 2- ) as a dense boron-10 source, and phenylboronic acid or RGD peptide as an active targeting moiety. Some hydroxy groups in PG were oxidized to carboxy groups (DND-PG-COOH) to conjugate the active targeting moiety. Some hydroxy groups in DND-PG-COOH were then transformed to azide to conjugate 10 B12 H11 2- through click chemistry. The nanodrugs were evaluated in vitro using B16 murine melanoma cells in terms of cell viability, BNCT efficacy and cellular uptake. As a result, the 10 B12 H11 2- moiety is found to facilitate cellular uptake probably due to its negative charge. Upon thermal neutron irradiation, the nanodrugs with 10 B12 H11 2- moiety exhibited good anticancer efficacies with slight differences with and without targeting moiety.

Observing ice structure of micron-sized vapor-deposited ice with an x-ray free-electron laser.

The direct observation of the structure of micrometer-sized vapor-deposited ice is performed at Pohang Accelerator Laboratory x-ray free electron laser (PAL-XFEL). The formation of micrometer-sized ice crystals and their structure is important in various fields, including atmospheric science, cryobiology, and astrophysics, but understanding the structure of micrometer-sized ice crystals remains challenging due to the lack of direct observation. Using intense x-ray diffraction from PAL-XFEL, we could observe the structure of micrometer-sized vapor-deposited ice below 150 K with a thickness of 2-50 µm grown in an ultrahigh vacuum chamber. The structure of the ice grown comprises cubic and hexagonal sequences that are randomly arranged to produce a stacking-disordered ice. We observed that ice with a high cubicity of more than 80% was transformed to partially oriented hexagonal ice when the thickness of the ice deposition grew beyond 5 µm. This suggests that precise temperature control and clean deposition conditions allow µm-thick ice films with high cubicity to be grown on hydrophilic Si3N4 membranes. The low influence of impurities could enable in situ diffraction experiments of ice nucleation and growth from interfacial layers to bulk ice.

Tumor Eradication by Boron Neutron Capture Therapy with 10 B-enriched Hexagonal Boron Nitride Nanoparticles Grafted with Poly(Glycerol).

Boron neutron capture therapy (BNCT) has emerged as a treatment modality with high precision and efficacy of intractable tumors. At the core of effective tumor BNCT are 10 B carriers with facile preparation as well as advantageous pharmacokinetic and therapeutic profiles. Herein, the design and preparation of sub-10 nm 10 B-enriched hexagonal boron nitride nanoparticles grafted with poly(glycerol) (h-10 BN-PG), and their application to cancer treatment by BNCT are reported. By virtue of their small particle size and outstanding stealth property, h-10 BN-PG nanoparticles accumulate efficiently in murine CT26 colon tumors with a high intratumor 10 B concentration of 8.8%ID g-1 or 102.1 µg g-1 at 12 h post-injection. Moreover, h-10 BN-PG nanoparticles penetrate into the inside of the tumor parenchyma and then are taken up by the tumor cells. BNCT comprising a single bolus injection of h-10 BN-PG nanoparticles and subsequent one-time neutron irradiation results in significant shrinkage of subcutaneous CT26 tumors. h-10 BN-PG-mediated BNCT not only causes direct DNA damage to the tumor cells, but also triggers pronounced inflammatory immune response in the tumor tissues, which contributes to long-lasting tumor suppression after the neutron irradiation. Thus, the h-10 BN-PG nanoparticles are promising BNCT agents to eradicate tumor through highly efficient 10 B accumulation.

Molecular Dynamics Study on Crack Propagation in Al Containing Mg-Si Clusters Formed during Natural Aging.

The crack propagation behavior of Al containing Mg-Si clusters is investigated using molecular dynamics (MD) simulations to demonstrate the relationship between the natural aging time in Al-Si-Mg alloys and ductility. Experimental results show that the elongation at failure decreases with natural aging. There are few studies on the relationship between natural aging and ductility because of the difficult observation of Mg-Si clusters. To solve the difficulty, cracked Al containing Mg-Si clusters of varying sizes are assumed for the MD simulations. A larger Mg-Si cluster in Al results in earlier crack opening and dislocation emission. Moreover, as the Mg-Si cluster size increases, the stress near the crack tip becomes more concentrated. This causes rapid crack propagation, a similar effect to that of crack tip sharpening. As a result of long-term natural aging, the cracks expand rapidly. The influence of geometry is also investigated. Crack lengthening and thickness reduction negatively impact the fracture toughness, with the former having a larger impact than the latter. Although there are several discrepancies in the practical deformation conditions, the simulation results can help to more thoroughly understand natural aging in Al-Si-Mg alloys.

Effect of Geometrical Parameters of Microscale Particles on Particle-Stimulated Nucleation and Recrystallization Texture of Al-Si-Mg-Cu-Based Alloy Sheets.

The effects of the shapes (needle and round) and volume fractions (low and high) of microscale particles in Al-Si-Mg-Cu-based alloys on recrystallization behavior, texture evolution, mechanical properties, and formability are investigated. The recrystallized grain size decreases as the size and volume fraction of the particles decrease and increase, respectively, regardless of the particle shape. The investigated alloys with a relatively low volume fraction of 0.7 to 2.4 vol.% exhibit higher efficiency particle-stimulated nucleation (PSN) than alloys with a high volume fraction of 6.0 to 21.0 vol.%. This is because the interaction between the particles and dislocations cannot be greatly promoted when the volume fraction of the particles is large enough to form agglomerates. The sheets with round-shaped particles exhibit higher yield strength (YS) and elongation (EL) than sheets with needle-shaped particles. The improvement in YS is due to the combined effects of grain refinement and particle strengthening, and the EL is improved by reducing the probability of cracking at the tips of round-shaped particles. The sheets with round-shaped particles exhibit relatively higher average plastic strain ratio (r¯) and planar anisotropy (∆r) than the sheets with needle-shaped particles, owing to the development of Goss {110}<001> or rotated-Goss {110}<110> orientations.

Influence of the Composition and Vacancy Concentration on Cluster Decomposition Behavior in Al-Si-Mg Alloy: A Kinetic Monte Carlo Study.

The influence of cluster composition and the addition of vacancies on the decomposition behavior of clusters during artificial aging in Al-Si-Mg alloys were analyzed according to the kinetic Montel Carlo model. Clusters with a balanced composition (Mg/(Mg + Si) = 0.5) were the most difficult to decompose. In addition, the cluster decomposition was slower when more vacancies were added to the cluster. Among Si, Mg, and vacancies, vacancies most significantly affect decomposition. The clusters with Mg/(Mg + Si) ≤ 0.4 strongly trap vacancies, which can be classified as hardly decomposable vacancy-rich clusters. The clustering behavior during natural aging and the effect of pre-aging were analyzed using the Kinetic Monte Carlo model. Pre-aging slows down cluster formation due to the lowered vacancy concentration. In addition, the overall composition of the clusters changes to easily decomposable clusters after pre-aging. Thus, not only is the number of clusters reduced but also the clusters are more easily decomposable when pre-aging is performed.

Polyglycerol Functionalized 10 B Enriched Boron Carbide Nanoparticle as an Effective Bimodal Anticancer Nanosensitizer for Boron Neutron Capture and Photothermal Therapies.

Boron neutron capture therapy (BNCT) is a non-invasive cancer treatment with little adverse effect utilizing nuclear fission of 10 B upon neutron irradiation. While neutron source has been developed from a nuclear reactor to a compact accelerator, only two kinds of drugs, boronophenylalanine and sodium borocaptate, have been clinically used for decades despite their low tumor specificity and/or retentivity. To overcome these challenges, various boron-containing nanomaterials, or "nanosensitizers", have been designed based on micelles, (bio)polymers and inorganic nanoparticles. Among them, inorganic nanoparticles such as boron carbide can include a much higher 10 B content, but successful in vivo applications are very limited. Additionally, recent reports on the photothermal effect of boron carbide are motivating for the addition of another modality of photothermal therapy. In this study, 10 B enriched boron carbide (10 B4 C) nanoparticle is functionalized with polyglycerol (PG), giving 10 B4 C-PG with enough dispersibility in a physiological environment. Pharmacokinetic experiments show that 10 B4 C-PG fulfills the following three requirements for BNCT; 1) low intrinsic toxicity, 2) 10 B in tumor/tumor tissue (wt/wt) ≥ 20 ppm, and 3) 10 B concentrations in tumor/blood ≥ 3. In vivo study reveals that neutron irradiation after intravenous administration of 10 B4 C-PG suppresses cancer growth significantly and eradicates cancer with the help of near-infrared light irradiation.

Preparation and Characterization of Metastable trans-Dinitrogen Tetroxide.

Under atmospheric conditions, NO2 is in equilibrium with its dimers, N2O4, which can exist in the form of constitutional isomers and stereoisomers whose relative stabilities and reactivities are still being debated. Experimental limitations facing the spectroscopic characterization of the isomers of N2O4 prevent us from determining their relative contributions to reaction mechanisms possibly causing discrepancies in the reported reaction orders and rates. Using reflection-absorption infrared spectroscopy, molecular beam deposition, and matrix isolation techniques, it is shown that the relative abundances of NO2 and its dimers can be controlled by heating or cooling the deposited gas. The comparison of spectra acquired from samples prepared using molecular beam deposition with those obtained using tube dosing deposition demonstrates how the N2O4 isomer distributions are sensitive to details of the experimental conditions and sample preparation protocols. These observations not only provide a better understanding of a possible source for the disagreements found in the literature, but also a methodology to control and quantify the chemical speciation in NO2 vapors in terms of the relative abundances of NO2 and of the various isomers of N2O4.

The Effect of Solidification Rate on the Corrosion Resistance of Die-Cast AZ91 Magnesium Alloy.

To increase the utilization of die-cast Mg alloys with various shapes in a variety of environments, the corrosion behaviors of commercial die-cast Mg alloys with different thicknesses were investigated in neutral and alkali solutions at ambient temperature. A decrease in the thickness of a specimen leads to an increase in cooling and solidification rates, which, in turn, decreases the size of the eutectic ß phases and the interphase distance, thus improving the hardness of the specimen. Specimens with relatively large ß phases were more corroded under neutral conditions due to severe galvanic corrosion at the interface between α-Mg and the ß phases, whereas they were protected by passivation films formed on the substrate in the alkaline solution. However, in the case of the alloy with thin thickness and high solidification rate, the fine ß phases improved corrosion resistance by forming a net structure that acted as a barrier to corrosion propagation of the α matrix. These results suggest that the size and distribution of the eutectic phases should be appropriately controlled, depending on the environment.

Fatigue Behavior of an AM50 Die-Casting Alloy Anodized by Plasma Electrolytic Oxidation.

While an anodizing process is essential for magnesium alloys to be used under corrosive environments, it sometimes stimulates a fatigue fracture that initiates at the interface between the coating layer and the substrate. In this study, a plasma electrolyte oxidation (PEO) technique was employed to provide excellent adhesion between the anodizing layer and the AM50 die-cast by applying an extremely high dielectric discharge in an alkaline phosphate electrolyte, and its effect on corrosion and fatigue behaviors was investigated. The stress intensity factor at the fatigue limit was estimated to be 0.28 MPam0.5. The specimen anodized using the PEO technique exhibits enhanced strength and corrosion resistance compared to the unanodized counterpart. Furthermore, it shows a relative fatigue life in spite of the thick anodizing layer because the crack initiates from the interface, not from the pore near the interface.

Is Self-Determined Motivation a Useful Agent to Overcome Perceived Exercise Barriers in Patients With Type 2 Diabetes Mellitus?

Background: Devising a program to increase physical activity (PA)/exercise behavior in patients with type 2 diabetes mellitus (T2DM) can meet with limited effectiveness in real-world settings because of the variety of barriers to PA/exercise that individuals need to overcome. An alternative approach is to explore whether targeting motivation as a facilitator may be effective to increase PA/exercise. This study aimed to understand attitudes toward perceived barriers to PA/exercise by examining individual levels of motivation, grounded on self-determination theory, in patients with T2DM. Methods: This study used an integrated approach combining qualitative and quantitative analysis. Sixteen patients with T2DM were grouped (n = 8 for each group) into either a higher self-motivation (HSM) or lower self-motivation (LSM) group via the Relative Autonomy Index. Thematic and deductive analysis were used to identify attitudes based on ten preconceived barrier themes: apathy, dislike, no priority, lack of support, health problems, lack of knowledge, unfavorable environment, tiredness, lack of time, and financial constraints. Quantitative analysis was to assess statistical differences in the volume of PA/exercise across the two groups, and a mixed-methods analysis was employed to highlight unique cases. Results: Patients in the HSM group expressed positive attitudes toward barriers to PA/exercise, while patients in the LSM group expressed a greater degree of hindrance. Although regular PA/exercise is necessary for T2DM management, patients with LSM considered PA/exercise a lesser priority displaying negative attitudes such as apathy and dislike. Conversely, patients with HSM placed greater emphasis on the benefits of PA/exercise regardless of apathy and dislike. Lack of time and health problems were commonly reported in both groups. The volume of PA/exercise corresponded to motivation levels, but there were some unique cases which arose from active commuting habits and severe health problems. Conclusion: These findings provide insights on how attitudes to perceived barriers to PA/exercise differ by levels of motivation. One insight was that examining motivation should be an essential consideration when designing practical strategies to overcome PA/exercise barriers in patients with T2DM. Lack of time and health problems exist regardless of motivation levels. Future research requires a tailored approach to managing barriers to PA/exercise in patients with T2DM.

Proton Transport and Related Chemical Processes of Ice.

Excess protons play a key role in the chemical reactions of ice because of their exceptional mobility, even when the diffusion of atoms and molecules is suppressed in ice at low temperatures. This article reviews the current state of knowledge on the properties of excess protons in ice, with a focus on the involvement of protons in chemical reactions. The mechanism of efficient proton transport in ice, which involves a proton-hopping relay along the hydrogen-bond ice network and the reorientation of water, is discussed and compared with the inefficient transport of hydroxide in ice. Distinctly different properties of protons residing in the ice interior and on the ice surface are emphasized. Recent observations of the spontaneous occurrence of reactions in ice at low temperatures, which include the dissociation of protic acids and the hydrolysis of acidic oxides, are discussed with regard to the kinetic and thermodynamic effects of mobile protons on the promotion of unique chemical processes of ice.

Effect of Protein Corona on Mitochondrial Targeting Ability and Cytotoxicity of Triphenylphosphonium Conjugated with Polyglycerol-Functionalized Nanodiamond.

Functionalization of nanoparticles (NPs) with targeting moieties has a high potential to advance precision nanomedicine. However, the targeting moieties on a NP surface are known to be masked by a protein corona in biofluids, lowering the targeting efficiency. Although it has been demonstrated at the cellular level, little is known about the influence of the protein corona on the subcellular targeting. Herein, we adopted triphenylphosphonium (TPP) as a mitochondrial targeting moiety and investigated the effects of protein coronas from fetal bovine serum and human plasma on its targeting ability and cytotoxicity. Specifically, we introduced TPP in low (l) and high (h) densities on the surface of nanodiamond (ND) functionalized with polyglycerol (PG). Despite the "corona-free" PG interface, we found that the TPP moiety attracted proteins to form a corona layer with clear linearity between the TPP density and the protein amount. By performing investigations on human cervix epithelium (HeLa) and human lung epithelial carcinoma (A549) cells, we further demonstrated that (1) the protein corona alleviated the cytotoxicity of both ND-PG-TPP-l and -h, (2) a smaller amount of proteins on the surface of ND-PG-TPP-l did not affect its mitochondrial targeting ability, and (3) a larger amount of proteins on the surface of ND-PG-TPP-h diminished its targeting specificity by restricting the NDs inside the endosome and lysosome compartments. Our findings will provide in-depth insights into the design of NPs with active targeting moiety for more precise and safer delivery at the subcellular level.

Recent Progress in the Manipulation of Molecules with DC Electric Fields.

The structure and reactivity of a molecule in the condensed phase are governed by its intermolecular interactions with the surrounding environment. The multipole expansion of each molecule in the condensed phase indicates that the intermolecular interactions are essentially electrostatic (e.g., ion-dipole, dipole-dipole, dipole-quadrupole, dipole-induced dipole). The electrostatic field is a fundamental language of intermolecular communications. Therefore, understanding the influence of the electrostatic field on a molecule, that is, the mechanisms by which an electrostatic field manipulates a molecule, from the perspective of molecular structure, energy states, and dynamics is indispensable for illustrating and, by extension, controlling the chemistry in molecular systems.In this Account, we describe the recent progress made in manipulation of molecular processes using an external DC electrostatic field. An electrostatic field with unprecedentedly high strength (≤4 × 108 V/m) was applied in a controlled manner across a molecular film sample using the ice film nanocapacitor method. This field strength is comparable in magnitude to that of weak intermolecular interactions such as van der Waals interactions in the condensed phases. The samples were prepared using a thin film growing technique in vacuum to obtain the desired chemically tailored molecular systems. The examples of prepared systems included small molecules and molecular clusters isolated in cryogenic Ar matrices, frozen molecular films in amorphous or crystalline phase, and interfaces of multilayered molecular films. The response of the molecules to the external field was monitored by reflection-absorption infrared spectroscopy. This approach allowed us to investigate a variety of molecular systems with various intermolecular strength and environments under the influence of strong electrostatic fields. The range of observed molecular behaviors includes the manipulation of molecular orientation, intramolecular dynamics, and proton transfer reactions as an example of stereodynamic control of chemical reactivity. These observations improve our understanding of molecular behaviors in strong electric fields and broaden our perspective on electrostatic manipulation of molecules. This information is also relevant to a variety of research topics in physical and biological sciences where electric fields play a role in molecular and biological functions.

Electric Field Effect on Condensed-Phase Molecular Systems. X. Interconversion Dynamics and Vibrational Stark Effect of Hydrogen Chloride Clusters in an Argon Matrix.

In this study, the effect of a strong (≤4 × 108 V·m-1) dc electric field on hydrogen chloride (HCl) dimers and trimers isolated in a solid argon matrix has been investigated using the ice film nanocapacitor and reflection-absorption infrared spectroscopy methods. The H-Cl vibrational bands of the HCl dimers showed a linear Stark frequency shift and an increased intensity under the applied electric field, and these changes were reversible with the electric field strength. This behavior indicated that the dimers were reoriented by the applied electric field. The reorientation occurred via tunneling inversion of individual HCl subunits of the dimer, which interconverted the proton-accepting and -donating HCl subunits, as observed for the heterodimers HCl-DCl and DCl-HCl. The interconversion of dimers could occur even at low electric field strength (∼107 V·m-1) and was almost complete above the field strength of 1.0 × 108 V·m-1. In contrast, the asymmetric H-Cl stretching bands of the HCl trimers exhibited Stark broadening under the influence of the electric field without a shift in frequency or change in intensity. This behavior indicated that the cyclic structure of the HCl trimer was stable even when subjected to a strong electric field. The Stark sensitivity factor (Δµ) of H-Cl vibrations was deduced from the Stark effect analysis of the HCl dimer and trimer bands, which gave the following: ΔµD1 = 2.3 ± 0.2 cm-1/(108 V·m-1) for the proton-acceptor subunit of the dimer, ΔµD2 = 5.1 ± 0.5 cm-1/(108 V·m-1) for the proton-donor subunit of the dimer, and ΔµT = 4.5 ± 0.5 cm-1/(108 V·m-1) for the asymmetric stretching vibration of the cyclic trimer.

The frequency-domain infrared spectrum of ammonia encodes changes in molecular dynamics caused by a DC electric field.

Ammonia is special. It is nonplanar, yet in v = 1 of the umbrella mode (ν2) its inversion motion is faster than J = 0↔1 rotation. Does the simplicity of the Chemist's concept of an electric dipole moment survive the competition between rotation, inversion, and a strong external electric field? NH3 is a favorite pedagogical example of tunneling in a symmetric double-minimum potential. Tunneling is a dynamical concept, yet the quantitative characteristics of tunneling are expressed in a static, eigenstate-resolved spectrum. The inverting-umbrella tunneling motion in ammonia is both large amplitude and profoundly affected by an external electric field. We report how a uniquely strong (up to 108 V/m) direct current (DC) electric field causes a richly detailed sequence of reversible changes in the frequency-domain infrared spectrum (the v = 0→1 transition in the ν2 umbrella mode) of ammonia, freely rotating in a 10 K Ar matrix. Although the spectrum is static, encoded in it is the complete inter- and intramolecular picture of tunneling dynamics.

Fast and Scalable Hydrodynamic Synthesis of MnO2/Defect-Free Graphene Nanocomposites with High Rate Capability and Long Cycle Life.

The integration of metal oxides and carbon materials provides a great potential for enhancing the high energy and power densities of supercapacitors, but the rational design and scalable fabrication of such composite materials still remain a challenge. Herein, we report a fast, scalable, and one-pot hydrodynamic synthesis for preparing ion conductive and defect-free graphene from graphite and MnO2/graphene nanocomposites. The use of this hydrodynamic method using Taylor-Couette flow allows us to efficiently fast shear-exfoliate graphite into large quantities of high-quality graphene sheets. Deposition of MnO2 on graphene is subsequently performed in a fluidic reactor within 10 min. The prepared MnO2/graphene nanocomposite shows outstanding electrochemical performances, such as a high specific capacitance of 679 F/g at 25 mV/s, a high rate capability of 74.7% retention at an extremely high rate of 1000 mV/s, and an excellent cycling characteristic (∼94.7% retention over 20 000 cycles). An asymmetric supercapacitor device is fabricated by assembling an anode of graphene and a cathode of MnO2/graphene, which resulted in high energy (35.2 W h/kg) and power (7.4 kW/kg) densities (accounting for the mass of both electrodes and the electrolyte) with a high rate capability and long cycle life.

Entropy-Driven Spontaneous Reaction in Cryogenic Ice: Dissociation of Fluoroacetic Acids.

Chemical reactions are extremely difficult to occur in ice at low temperature, where atoms and molecules are frozen in position with minimal thermal energy and entropy. Contrary to this general behavior, certain weak acids including fluoroacetic acids dissociate spontaneously and more efficiently in cryogenic ice than in aqueous solution at room temperaure. The enhanced reactivity of weak acids is an unexpected consequence of proton-transfer equilibrium in ice. The configurational entropy of protons in ice shifts the acid dissociation equilibrium forward. This configurational entropy, although a solid-state property, is comparatively large in magnitude with the entropy of vaporization and can effectively drive proton-transfer reactions in ice.

Electric Field Effect on Condensed-Phase Molecular Systems. VI. Field-Driven Orientation of Hydrogen Chloride in an Argon Matrix.

The orientation state of hydrogen chloride (HCl) molecules in a solid argon matrix was reversibly controlled by applying an external electric field of up to 4 × 108 V·m-1 using the ice film capacitor method. The rovibrational transitions of the field-oriented HCl were measured by reflection absorption infrared spectroscopy with p-polarized light. Upon application of the external field, free rotation of HCl inside the matrix gradually changed to perturbed rotation and then to a pendular state harmonically bound in the Stark potential well. Further increase in the field strength increased the degree of dipole alignment along the field direction, approaching an asymptotically perfect orientation of the molecules with an average tilt angle of <30° at a field strength above 1 × 108 V·m-1.