Superficial Excess Research Articles

Differentiation and Treatment of Chronic Renal Failure Based on the Theory of "Peace and Balance"

Chronic renal failure is slow, the course of disease is long, and it is difficult to heal. At present, modern medicine is faced with many difficulties in treatment, and it is difficult to break through. The Chinese medicine treats the symptoms according to the whole concept and has obtained good curative effect. Although the pathogenesis of the disease is complicated, in the whole process of onset, deficiency in origin and excess in superficiality is still the most critical. It is often caused by deficiency of spleen and kidney, disorder of liver ascending and lung descending, combined with phlegm-dampness and stasis toxin, and the disturbance of internal and external wind. Consequently. It is necessary to treat multiple viscera at the same time, and treat both manifestation and root cause of disease. The theory of "Peace and Balance" fully interprets the overall concept of Chinese medicine, we advocate "aim for peace" and Incorporate "balance" throughout the entire treatment,to reach the balance of yin and yang. Therefore, this article will discuss the treatment based on syndrome differentiation of Chronic renal failure by the theory of "Peace and Balance".

Medication rule of traditional Chinese medicine for heart failure after myocardial infarction: based on data mining

This study aims to explore the medication rule of traditional Chinese medicine(TCM) for heart failure after myocardial infarction via data mining. To be specific, articles on the treatment of the disease with Chinese medicine were retrieved from CNKI, Wanfang, VIP, and SinoMed and related information was collected. A database was created with Microsoft Excel 2019, and SPSS Clementine 12.0 and IBM SPSS Statistics 23.0 were applied for association rules analysis, cluster analysis, and factor analysis. Finally, a total of 81 TCM prescriptions were screened out, involving 91 medicinals with cumulative use frequency of 740. The main syndromes were Qi deficiency and blood stasis, Yang Qi deficiency and blood stasis together with retained morbid fluid, deficiency of both Qi and Yin and blood stasis. The medicinals with high-frequency were Astragali Radix, Salviae Miltiorrhizae Radix et Rhizoma, Ginseng Radix et Rhizoma, Poria, and Aconiti Lateralis Radix Praeparata. The effects of the medicinals were tonifying deficiency, activating blood and resolving stasis, and promoting urination and draining dampness. The association rules analysis yielded "Astragali Radix-Salviae Miltiorrhizae Radix et Rhizoma" "Astragali Radix-Aconiti Lateralis Radix Praeparata-Salviae Miltiorrhizae Radix et Rhizoma" "Aconiti Lateralis Radix Praeparata-Ginseng Radix et Rhizoma-Salviae Miltiorrhizae Radix et Rhizoma-Astragali Radix" combinations. Cluster analysis yielded 6 basic formulas for heart failure after myocardial infarction. Factor analysis extracted a total of 8 common factors. Heart failure after myocardial infarction is characterized by the syndrome of deficiency in nature and excess in superficiality. The core pathogenesis is "deficiency" "stasis" "retained morbid fluid", particularly "deficiency". This disease is closely related to the heart, lung, and spleen. The basic treatment principle is replenishing Qi and activating blood, and warming Yang, excreting water, and nourishing yin should also be emphasized. The common basic prescriptions, such as Siwu Decoction, Shengmai Powder, Xuefu Zhuyu Decoction, Linggui Zhugan Decoction, and Shenfu Decoction, have been discovered. This study provided data for clinical medication and drug development for heart failure after myocardial infarction.

Clinical Experience of Acupuncture Treatment for Non-Alcoholic Fatty Liver Disease.

Based on the authors' clinical experience, the acupuncture treatment of non-alcoholic fatty liver disease mainly includes the following three aspects. (1) The etiology and pathogenesis of non-alcoholic fatty liver disease are based on “deficiency in origin and excess in superficiality.” The deficiency in origin means deficiency of the spleen and stomach, and the excess in superficiality is caused by hepatobiliary disorders. (2) The application of the theory of strengthening the spleen and mobilizing transportation should be considered for the treatment of non-alcoholic fatty liver disease by acupuncture and moxibustion. Therefore, the use of “treatment from the spleen” often has miraculous effects. (3) Skillful use of acupuncture, shallow acupuncture, acupoint thread embedding, and other traditional Chinese medicine therapies are used to regulate the liver and spleen. In addition, warm acupuncture is reused to warm the Yang and strengthen the body.

Preventing the Undesired Surface Veiling after Nanolime Treatments on Wall Paintings: Preliminary Investigations

During the last decades, the discovery of nanolime and its introduction in the field of Cultural Heritage has entailed a significant advance for the consolidation of historic wall paintings. Nevertheless, its use is not completely generalized yet within the conservation practitioner’s community due to its undesired white veiling deposit on the surface after treatment which usually covers the pictorial layer. Given the scarcity of existing literature which specify how to mitigate this undesired side-effect, the aim of this work is to carry out the first assessment of possible cleaning and treatment methods to eliminate those deposits and, at the same time, to analyse their effects on the consolidation properties. To do that, we have developed laboratory fresco wall paintings specimens. After applying an artificial ageing cycle to all of them, we consolidated them with CaloSil IP25, one of the most currently used commercial product in the practice. The elimination of the whitish deposits has been investigated with different methods: (1) wiping off the superficial excess of product immediately after each application during the treatment; (2) mechanical cleaning (scalpel) after consolidation; chemical cleaning with rigid gels of water (3), ethylenediaminetetraacetic acid (EDTA) (4) and citric acid (5) after consolidation. The effectiveness of each cleaning method has been assessed by non-destructive methods before and after the consolidation, and repeated after cleaning, by measuring differences in colour, water absorption by capillarity (i.e., sponge test), superficial adhesion (i.e., Scotch Tape Test) and by quantifying the thickness of the deposits eliminated by means of photogrammetry. Results show that both the mechanical cleaning and the removal of the excess of product after each application during the treatment yielded the most promising results for conservation practice.

Complex network analysis of combination medication of patients with kidney malignant tumor based in real world

Kidney malignant tumor is a type of primary renal cell carcinoma, and mainly refers to renal cancer. The incidence of kidney cancer and the number of hospital cases in China have been increasing. Based on the clinical medicine information of patients in the hospital information system(HIS) database of 37 hospitals in China, the combined medication of patients with kidney malignant tumor were analyzed by Tabu search algorithm, so as to analyze the combined medication of patients with kidney malignant tumor in real world. A total of 7 095 patients with kidney malignant tumor were included, the ratio of males to females was 2.11∶1, and the ratio of male patients increased gradually with age. About 3 933 patients(55.43%) showed a superior effect among those patients. The common therapies of patients with kidney malignant tumor were anti-tumor therapies and symptomatic therapies, including anti-infection, regulation of electrolyte balance, sedation and analgesia, analgesic, regulation of gastrointestinal function. The whole population of patients with kidney malignant tumor were mostly treated with anti-tumor drugs combined with more symptomatic therapies, while the anti-tumor therapies of the superiority population of patients were less combined with other drugs, with less combined medication. The result may be related to the stage of tumor or individual response to the therapeutic regimen. No matter for the whole population or for the superiority population of patients with kidney malignant tumor, the therapies was mainly Western medicines. Based on the pathogenesis of deficiency in origin and excess in superficiality with kidney malignant tumor, Chinese subgroups with formula for clearing heat and removing toxicity, formula for vigorate Qi and replenish the blood, formula for regulate Qi and invigorate the blood, laxative and hemostatic were more commonly used. In the future, further studies shall be conducted for combined therapies for patients of different stages, so as to play the advantages of multi-target, overall regulation, toxicity reduction and efficacy enhancement of traditional Chinese medicine, improve the life quality of patients with kidney malignant tumor, prolong their life time, and improve the survival rate of patients.

Pi (Spleen)-deficiency syndrome in tumor microenvironment is the pivotal pathogenesis of colorectal cancer immune escape.

Cancer immunoediting consists of three sequential phases: elimination, equilibrium, and escape. For colorectal adenoma-carcinoma sequence, the adenoma dysplastic progression may represent an equilibrium phase and the cancer stage as escape phase. Immune system eliminates transformed enterocytes by destroying them at first, sculpts them at the same time and selects the variants subsequently that are no longer recognized and insensitive to immune effectors, and finally induces immunosuppressive state within the tumor microenvironment that facilitates immune escape and tumor outgrowth. Immunosuppression and inflammation are the two crucial features of Pi (Spleen)-deficiency. Classic quotations, immune evidence and clinical observations suggest that Spleen (but not other organs) deficiency is the key pathogenesis of colorectal cancer (CRC) microenvironment. Weakness of old age, immunosuppressive cytokines from chronic inflammation, tumor-derived immunosuppressive factors and surrendered immune cells-regulatory T cells, myeloid-derived suppressor cells and tumor associated macrophages (TAMs) constitutes CRC microenvironment of Pi-deficiency. Furthermore, excess in superficiality, such as phlegm stagnation, blood stasis and toxin accumulation are induced by chronic inflammation on the basis of asthenia in origin, an immunosuppressive state. Great masters of Chinese medicine emphasize that strengthen Pi is the chief therapeutic principle for CRC which receives good therapeutic effects. So, Pi-deficiency based syndrome is the pivotal pathogenesis of tumor microenvironment. The immunosuppressive microenvironment facilitates immune escape which play an important role in the transition from adenoma to adenocarcinoma. There are some signs that strengthen Pi based treatment has potential capacity to ameliorate tumor environment. It might be a novel starting point to explore the mechanism of strengthen Pi based therapy in the prevention and treatment of CRC through regulation of tumor environment and immunoediting.

Analysis of TCM syndrome elements and relevant factors for senile diabetes

ObjectiveTo explore the laws governing the distribution of TCM syndrome elements (SEs) of senile diabetes (SD) and their relationship to relevant factors. MethodAn investigation of patients who met the inclusion criteria was conducted by trained doctors, using case report forms. All related data were collected, including body mass index (BMI =body weight [kg]/height2 [m]), glycated hemoglobin, illness course, complications, symptoms, and tongue and pulse manifestation. The SEs of each patient were judged by three qualified associate chief physicians independently. ResultThe main SEs of SD are Yin deficiency, Qi deficiency, blood stasis, and phlegm turbidity. Yin deficiency, Qi deficiency, blood stasis, and phlegm turbidity are most commonly seen among 4-SE combinations. Yang deficiency is typically related to illness course and BMI, phlegm turbidity to hypertension and hyperlipidemia, excessive heat to diabetic microangiopathy, and blood stasis to illness course and diabetic macroangiopathy. ConclusionSD pathogenesis has a deficiency in origin and excess in superficiality. Deficiency syndrome mainly manifests as deficiency of both Qi and Yin, and concurrently in Yang deficiency. Excess syndrome is characterized by blood stasis and phlegm turbidity. SE analysis provides a basis for the prevention and treatment of SD with Traditional Chinese Medicine (TCM) and lays the foundation for objectively evaluating multicentric clinical research for SD in TCM.

Retrospective study on Professor Zhongying Zhou's experience in Traditional Chinese Medicine treatment on diabetic nephropathy

ObjectiveTo study and analyze the etiology and pathogenesis, diagnosis and prescription for cases of diabetic nephropathy (DN) treated by Professor Zhongying Zhou (Prof. Zhou) with the help of dada mining technique, so as to inherit his clinical experience and academic thoughts. MethodsAfter pretreatment of the medical record information, statistical software SPSS 13.0 was used to analyze and process the standardized data using the descriptive analysis, cluster analysis and association rules. ResultsNinety-four entries derived from Traditional Chinese Medicine (TCM) four-diagnostic information were selected. Through data mining, the highest frequency was yellow-thin-greasy tongue coating, followed by dark tongue, and then by thready-slippery pulse. The main self-conscious symptoms were limb numbness, dry mouth, frequent micturition, etc. With respect to pathogenesis, the etiology related to kidney reached 73.46%. The frequency of pathological factors for deficiency, blood stasis, heat, dampness, phlegm and dryness were 137.65%, 80.25%, 78.40%, 48.77%, 21.60%, and 14.20% respectively. A total of 236 kinds of herbs were used 2913 person times, averaging 17.98 herbs per prescription. ConclusionThe pathological location of DN is in the kidney. The pathogenesis of the disease is deficiency in origin and excess in superficiality, the former of which include deficiency of the liver and kidney, and deficiency of both Qi and Yin. The main pathological factors are blood stasis, heat, dampness, phlegm, and dryness; and they act upon each other to form the complex pathogenesis in terms of blood stasis-heat, dampness-heat, phlegm-heat, and dryness-heat. All the above factors are always crucial in the aggravation of DN throughout the whole course of its pathological evolution.

A contribution to the mechanics and thermodynamics of surface growth. Application to bone external remodeling

The surface growth of biological tissues is presently analyzed at the continuum scale of tissue elements, adopting the framework of the thermodynamics of surfaces. Growth is assumed to occur in a moving referential configuration (called the natural configuration), considered as an open evolving domain exchanging mass, work, and nutrients with its environment. The growing surface is endowed with a superficial excess concentration of moles, which is ruled by an appropriate kinetic equation. From a thermodynamic framework of surface growth, the equilibrium equations are derived in material format from a suitable thermodynamic potential, highlighting the material surface forces for growth based on a surface Eshelby stress. Those forces depend upon a surface Eshelby stress, the curvature tensor of the growing surface, the gradient of the chemical potential of nutrients, and a surface force field. Application of the developed formalism to bone external remodeling highlights the interplay between transport phenomena and generation of surface mechanical forces. The model is able to describe both bone growth and resorption, according to the respective magnitude of the chemical and mechanical contributions to the material surface driving force for growth.

Analysis of Clinical Syndromes in 47 Patients with Pancreatic Cancer at Late Stage

To analyze the law governing the distribution of traditional Chinese medicine (TCM) syndromes of pancreatic cancer. The authors used retrospective study to statistically analyze TCM syndromes of patients, separated complex syndromes and calculated the frequency of appearance of single syndromes. The patients mainly suffered from 4 syndromes: blood stasis syndrome, qi stagnation syndrome, qi (yang) deficiency syndrome, and phlegm dampness syndrome. The distribution of syndromes is rarely related to sex, age and morbid site of patients. Owing to complicated distribution of its syndromes, pancreatic cancer should be diagnosed and treated according to its characteristics of deficiency in origin and excess in superficiality.

Syndrome analysis on patients of chronic hepatitis B treated by Lamivudine

Objective To study syndrome and pathogenesis of patients of chronic hepatitis B treated by Lamivudine. Methods By Observing clinical information of Chinese medical symptoms, physical signs,tongue and pulse, TCM syndrome of 103 patients of Chronic Hepatitis B treated by Lamivudine were differentiated by two attending doctors and analyzed. Results Patten of 103 patients were: spleen deficiency and damp-heat (20.38%), spleen deficiency (20.38%), endoretention of damp-heat (19.41%), liver depression and spleen deficiency(13.59%), liver yin deficiency (8.73%); Syndrome of 103 patients were: spleen deficiency (47.57%), damp-heat (43.68%), liver depression (11.65%), liver yin deficiency (10.67%), blood stasis (8.73%), kidney yin deficiency (3.88%). Conclusion Pathogenesis of patients of chronic hepatitis B treated by Lamivudine was spleen-liver-kidney deficiency, and endoretention of damp-heat; Nature of disease was deficiency in origin and excess in superficiality, and simultaneous deficiency and excess; Common syndromes were spleen deficiency, damp-heat, liver depression, liver yin deficiency, blood stasis, and kidney yin deficiency. Key words: Chronic Hepatitis B; Lamivudine; Syndrome; Pathogenesis

The Effect of Adsorbed Sodium Dodecylsulfate at the Alumina–Water Interface on the Luminescence Quenching of Tris(2,2′-bipyridine) ruthenium(II) by Nitrophenols

The luminescence quenching of tris(2,2′-bipyridine)ruthenium(II) (Ru(bpy)32+) by 2-, 3-, and 4-nitrophenol (NO2PhOH) was studied in the absence and presence of aggregates of sodium dodecyl sulfate (SDS) in the bulk solution and in the adsorbed state on α-alumina at pH 2. At this pH, the alumina has a superficial excess of positive charge. The uncorrected luminescence spectrum of Ru(bpy)32+ did not show any spectral shift in alumina suspension in the absence of SDS in relation to the spectrum in aqueous solution at pH 2 (λmax=609 nm). In the presence of 1 g/L alumina and concentrations of SDS between 0.6 and 0.8 mM and the critical micellar concentration (CMC), the surfactant forms surface aggregates—hemimicelles or admicelles. In these surface aggregates, the emission spectrum showed a red shift (λmax=637 nm). At SDS concentrations higher than the CMC, the surfactant forms micelles in the bulk solution and surface aggregates onto α-alumina. However, from the spectral shift observed with the increase in SDS concentration, it seems that, at high surfactant concentrations in the bulk, the metallic complex prefers to remain in the micellar instead of in the hemimicellar phases. The emission maximum in micelles was in 627 nm. The Stern-Volmer constants (KSV) of luminescence quenching were determined from steady-state emission intensity measurements at the maximum of emission in each case. The luminescence quenching of Ru(bpy)32+ showed that the NO2PhOHs are incorporated into both types of aggregates. On the basis of the KSV values as a function of the SDS concentration, the process of luminescence quenching of Ru(bpy)32+ by these compounds is more efficient in premicelles/micelles than in the surface aggregates onto α-alumina. This was observed up to a concentration of 5 mM SDS. These results can be interpreted as an effect of the increase in polarity of the micellar microenvironment on the electron-transfer mechanism for the quenching process. At SDS concentrations higher than 5 mM, the plot of KSV vs SDS concentration in the presence of 1 g/L alumina is shifted to higher SDS concentrations in relation to the observed plot in the absence of 1 g/L alumina. This fact can be explained in terms of the surfactant that forms surface aggregates onto alumina which do not contain the metallic complex.

Effect of Adsorbed Cetyltrimethylammonium at the Alumina–Water Interface on the Luminescence Quenching of Tris(2,2′-bipyridine)ruthenium(II) by 2,6-Dimethylphenolate Ions

The luminescence quenching of tris(2,2′-bipyridine)ruthenium(II) [Ru(bpy)2+3] by ion 2,6-dimethylphenolate (2,6-DMP), in the presence of cetyltrimethylammonium chloride (CTAC) micelles or monomers of the surfactant absorbed on alumina at pH 12, was studied. At this pH, the alumina has a superficial excess of negative charge. The quenching rate constants were determined from luminescence measurements, steady-state emission intensity, or luminescence lifetime. The luminescence spectrum of Ru(bpy)2+3did not show any shift in the presence of alumina in suspension with or without CTAC adsorbed on the alumina. The ultraviolet spectrum of 2,6-DMP did not show a spectral shift in the above systems, alumina suspension and CTAC–alumina suspension, either. From these facts, it was concluded that the metallic complex and the anionic 2,6-DMP do not interact with both systems. However, the efficiency of quenching by 2,6-DMP decreased in the presence of dispersed alumina at pH 12. The opposite effect, an increase in quenching efficiency, was observed when CTAC was adsorbed on alumina in concentrations lower than or similar to the critical micelle concentration (CMC). These results are discussed in terms of (1) the electrical interaction of the negative alumina surface with both partners in the quenching pair, Ru(bpy)2+3and 2,6-DMP anion, and (2) the neutralization of the surface charge by CTAC owing to the favorable alumina surface–surfactant electrostatic interaction. At CTAC concentrations higher than the CMC, the observed effect is that corresponding to the decrease in the quenching efficiency because of the micellar binding of 2,6-DMP ions.

First Example of Surfactants Enclosing a Semipolar Nitrogen−Boron Bond

We describe a new surfactant family whose hydrophilic head contains a semipolar N+−B- bond in a stable aminopropylborane structure. These compounds were synthesized by hydroboration of allylic amines with good yields (>90%). Parameters characterizing their surface activity (critical micelle concentration, surface tension, superficial excess, molecular area at the water−air interface) along with the phase diagram in a water−isooctane−butanol system were determined. The compounds show promise for use in organized molecular systems (OMS).

On the electrochemical behaviour of quinine at the mercury electrode in aqueous solutions

It is shown that the so-called “prewave” displayed by quinine in alkaline solutions is a misnomer. It has been identified as the narrow part of the polarization curve where the potential is such that quinine adsorption or reduction is absent, corresponding to an interphase whose inner layer is only populated by water molecules. This conclusion is supported by the absolute values of the charge densities, the shape of the current-time polarographic transients and the fact that extension of its potential domain is favoured by increasing the pH and/or lowering of the quinine concentration. Double-potential programmes have been used to investigate the kinetics of the adsorption-desorption process of quinine. It appears that desorption is controlled by a nucleation and growth mechanism of the Avrami type, while adsorption gives monotonic falling transients. The electroreduction of quinine has been investigated in part and some of the properties of the reduction product assessed (electro-oxidizability, adsorbability). Potential-step chronocoulometry gave a value of the superficial excess of quinine, which has been used to propose a model for the film structure. Inhibition experiments with quinine and its reduction product indicate that both surfactants act efficiently, but to a lesser extent than smaller aromatic bases, and the reduction product is a more active inhibitor than quinine itself.

On the electrochemical behaviour of quinine at the mercury electrode in aqueous solutions

It is shown that the so-called “prewave” displayed by quinine in alkaline solutions is a misnomer. It has been identified as the narrow part of the polarization curve where the potential is such that quinine adsorption or reduction is absent, corresponding to an interphase whose inner layer is only populated by water molecules. This conclusion is supported by the absolute values of the charge densities, the shape of the current-time polarographic transients and the fact that extension of its potential domain is favoured by increasing the pH and/or lowering of the quinine concentration. Double-potential programmes have been used to investigate the kinetics of the adsorption-desorption process of quinine. It appears that desorption is controlled by a nucleation and growth mechanism of the Avrami type, while adsorption gives monotonic falling transients. The electroreduction of quinine has been investigated in part and some of the properties of the reduction product assessed (electro-oxidizability, adsorbability). Potential-step chronocoulometry gave a value of the superficial excess of quinine, which has been used to propose a model for the film structure. Inhibition experiments with quinine and its reduction product indicate that both surfactants act efficiently, but to a lesser extent than smaller aromatic bases, and the reduction product is a more active inhibitor than quinine itself.

On the behaviour of molecules of the quinoline group at the water-mercury interface Part I. Electrocapillary study of the o-quinoline in solutions containing only an “inert” electrolyte

The present paper is the first of a series dedicated to the interfacial behaviour of several surfactants of the quinoline group, respectively in the absence and in the presence of coadsorbed anions. The present communication deals with the adsorption of quinoline (Q) itself at the mercury—water interface, in a medium such that coadsorption can be considered as negligible. Study of equilibrium adsorption has been based on measurements of interfacial tensions, charge densities and differential capacities as a function of the potential and the Q concentration. The experimental isotherms have been analysed with the help of Esin-Markov plots. In the range of sufficiently negative potentials, a compact film of invariant structure is observed, which remains stable up to a sharply defined cathodic desorption potential. At less negative potentials, the Esin-Markov plots, as well as the capacity—concentration—potential map, indicate that three different superficial structures may prevail, according to the domain of potential and concentration:o(1)water with dilute Q molecules lying flat;(2)a mixed aqueous layer which embodies both flat and standing Q molecules;(3)a film characterized by abnormally large values of the superficial excess, reflecting the presence of randomly distributed multilayered clusters. No clear evidence has been found for a stable compact layer of molecules lying flat. As can be expected, surface—pressure plots are non-congruent, in view of the variety of orientation and lateral forces involved with potential or concentration changes. Some data are presented which will be made fully explicit at a later stage (Parts IV and V of this series), where the various surfactants will be compared in terms of their molecular structure and dipole orientation. water with dilute Q molecules lying flat; a mixed aqueous layer which embodies both flat and standing Q molecules; a film characterized by abnormally large values of the superficial excess, reflecting the presence of randomly distributed multilayered clusters. No clear evidence has been found for a stable compact layer of molecules lying flat. As can be expected, surface—pressure plots are non-congruent, in view of the variety of orientation and lateral forces involved with potential or concentration changes. Some data are presented which will be made fully explicit at a later stage (Parts IV and V of this series), where the various surfactants will be compared in terms of their molecular structure and dipole orientation.

On the behaviour of molecules of the quinoline group at the water-mercury interface: Part I. Electrocapillary study of α-quinoline in solutions containing only an “inert” electrolyte

The present paper is the first of a series dedicated to the interfacial behaviour of several surfactants of the quinoline group, respectively in the absence and in the presence of coadsorbed anions. The present communication deals with the adsorption of quinoline (Q) itself at the mercury—water interface, in a medium such that coadsorption can be considered as negligible. Study of equilibrium adsorption has been based on measurements of interfacial tensions, charge densities and differential capacities as a function of the potential and the Q concentration. The experimental isotherms have been analysed with the help of Esin-Markov plots. In the range of sufficiently negative potentials, a compact film of invariant structure is observed, which remains stable up to a sharply defined cathodic desorption potential. At less negative potentials, the Esin-Markov plots, as well as the capacity—concentration—potential map, indicate that three different superficial structures may prevail, according to the domain of potential and concentration: o (1) water with dilute Q molecules lying flat; (2) a mixed aqueous layer which embodies both flat and standing Q molecules; (3) a film characterized by abnormally large values of the superficial excess, reflecting the presence of randomly distributed multilayered clusters. No clear evidence has been found for a stable compact layer of molecules lying flat. As can be expected, surface—pressure plots are non-congruent, in view of the variety of orientation and lateral forces involved with potential or concentration changes. Some data are presented which will be made fully explicit at a later stage (Parts IV and V of this series), where the various surfactants will be compared in terms of their molecular structure and dipole orientation.

The variation of the superficial excess of entropy in relation to the structure of water in sodium fluoride solutions

The mercury-NaF aqueous solutions interfacial tension has been measured at varying concentrations and temperatures. These results, associated with those of other authors [1,2], enable one to determine, without ambiguity, and for all accessible values of the electrode charge, the sign and the order of magnitude of the variation with the temperature of the superficial excess of entropy. The curves showing the variations of the superficial excess of concentration with the charge indicate a very slight specific adsorption of the fluoride ions at low temperatures which leads to a contribution of about 0.007 erg K −1 cm −2 to the entropy. These results have been compared with those forecast theoretically by Bockris and Habib [3] who schematically consider the interfacial layer of water as being composed of monomers and dimers, the latter being unaffected by the electrical field. Taking into account the variation with the temperature of the various factors contributing to the interfacial entropy, as envisaged by these authors, one finds a variation of −0.04 erg K t-1 cm −2 as compared with +0.14 erg K −1 cm −2 found experimentally. This reveals the shortcomings of the proposed model in spite of the good agreement obtained at one temperature for the variations with the charge. This model can therefore only be considered as acceptable if supplementary hypotheses are made as for example assuming interactions between the different molecular forms. One can also consider that this type of dimer or even larger aggregate such as those envisaged by Frumkin [4] and Parsons [5] for the interfacial water, consistutes a somewhat over simplified approach of the problem. The experimental results obtained and their examination in the light of recent theories show that the important problems of the structure of the interfacial water still remains unsolved. There is therefore a need for a statistical approach to these questions based the theories suggested for the volume, and also taking into account the influence of the substratum.

Ion hydration near air/water interfaces and the structure of liquid surfaces

Negative adsorption of ions, commonly observed at air-water interfaces, is examined in terms of models of restricted polarization of the solvent by ions at the interface and the structure of the liquid interface. The Born and other models of ionic hydration are applied to evaluate the self-energy of the ion arising in the region of solvent near its interface and in the vacuum or vapour beyond. The adsorption energy of an ion varies substantially with distance from the liquid interface so that a distribution of ions arises as a function of distance from the interface. Integration of this distribution gives an expression, and results, for the ionic surface excess. The diffuse-layer potential, which an unequal distribution of cations and anions give rise to, gives a contribution to the surface potential of the electrolyte solution at finite concentrations. Structural aspects of the liquid interface at which ions are negatively adsorbed are discussed in terms of Stefan's ratio and the superficial excess entropies of various liquid surfaces. These entropies are related to the cohesive energy densities of the bulk liquids. Ion solvent-structure co-sphere interactions with structured interfaces will lead to specificity of negative adsorption of ions.