Dynamic Surface Enrichment in Drying Thin-Film Binary Polymer Solutions.

Solution-cast, thin-film polymer composites find a wide range of applications, such as in the photoactive layer of organic solar cells. The performance of this layer crucially relies on its phase-separated morphology. Efficient charge-carrier extraction requires each of the components to preferentially wet one of the two electrodes. It is often presumed that the experimentally observed surface enrichment required for this is caused by specific interactions of the active ingredients with each surface. By applying a generalized diffusion model, we find the dynamics to also play an important role in determining which component accumulates at which surface. We show that for sufficiently fast evaporation the component with the smallest cooperative diffusivity accumulates at the free interface. Counterintuitively, depending on the interactions between the various components, this may be the smaller solute. Our comprehensive numerical and analytical study provides a tool to predict and control phase-separated morphologies in thin-film polymer composites.

A Landau-de Gennes theory for hard colloidal rods: Defects and tactoids.

We construct a phenomenological Landau-de Gennes theory for hard colloidal rods by performing an order parameter expansion of the chemical-potential dependent grand potential. By fitting the coefficients to known results of Onsager theory, we are not only able to describe the isotropic-nematic phase transition as function of density, including the well-known density jump, but also the isotropic-nematic planar interface. The resulting theory is applied in calculations of the isotropic core size in a radial hedgehog defect, the density dependence of linear defects of hard rods in square confinement, and the formation of a nematic droplet in an isotropic background.

Self-crowding induced phase separation in protein dispersions.

The coupling between protein conformation, molecular volume, and solution phase behaviour is studied theoretically for a two-state, coarse-grained protein model in which protein molecules can reversibly switch between a native and a non-native excited state. In the model, native and non-native conformers are represented by perfect spheres with different hard-core diameters. We presume the larger, non-native species to attract each other through some unspecified potential. We find that at low concentrations the native state is stabilised energetically and that at high concentrations the native state is again stabilised but this time by self-crowding, i.e., a lack of free volume. These two regimes are separated by two first-order transitions from a region where the non-native conformational state is prevalent, stabilised by attractive interactions between the proteins. The calculated phase diagram is very sensitive to even quite small differences in particle volumes and has unusual features, including the loss of a critical point if the size difference is sufficiently large.

Structuring of polymer solutions upon solvent evaporation.

The morphology of solution-cast, phase-separated polymers becomes finer with increasing solvent evaporation rate. We address this observation theoretically for a model polymer where demixing is induced by steady solvent evaporation. In contrast to what is the case for a classical, thermal quench involving immiscible blends, the spinodal instability initially develops slowly and the associated length scale is not time invariant but decreases with time as t(-1/2). After a time lag, phase separation accelerates. Time lag and characteristic length exhibit power-law behavior as a function of the evaporation rate with exponents of -2/3 and -1/6. Interestingly, at later stages the spinodal structure disappears completely while a second length scale develops. The associated structure coarsens but does not follow the usual Lifshitz-Slyozov-Wagner kinetics.

Implications of protein polymorphism on protein phase behaviour.

The phase behaviour of small globular proteins is often modeled by approximating them as spherical particles with fixed internal structure. However, changes in the local environment of a protein can lead to changes in its conformation rendering this approximation invalid. We present a simple two-state model in which protein conformation is not conserved and where the high-energy, non-native state is stabilised by pair-wise attractive interactions. The resulting phase behaviour is remarkably complex, non-universal and exhibits re-entrance. The model calculations show a demarcation between a regime where conformational transitioning is largely enslaved by phase separation and one where this is not the case. In the latter regime, which is characterised by a large free energy difference between the native and the non-native state, we deduce that the kinetics of the phase transition strongly depend on the average conformation of the proteins prior to their condensation. For condensation to occur in this regime within a dispersion of native proteins, nucleation of a cluster of proteins in the non-native state is required. We argue that our theory supports the distinction between common phase separation and the nucleated assembly of non-native supramolecular aggregates in protein dispersions.

Texture and shape of two-dimensional domains of nematic liquid crystals.

We present a generalized approach to compute the shape and internal structure of two-dimensional nematic domains. By using conformal mappings, we are able to compute the director field for a given domain shape that we choose from a rich class, which includes drops with large and small aspect ratios and sharp domain tips as well as smooth ones. Results are assembled in a phase diagram that for given domain size, surface tension, anchoring strength, and elastic constant shows the transitions from a homogeneous to a bipolar director field, from circular to elongated droplets, and from sharp to smooth domain tips. We find a previously unaccounted for regime, where the drop is nearly circular, the director field bipolar, and the tip rounded. We also find that bicircular director fields, with foci that lie outside the domain, provide a remarkably accurate description of the optimal director field for a large range of values of the various shape parameters.

Controlling the Cooperativity in the Supramolecular Polymerization of Ionic Discotic Amphiphiles via Electrostatic Screening.

In a combined experimental and theoretical approach, we investigate the supramolecular polymerization of ionic discotic amphiphiles into nanorods of varying mean length, depending on the temperature and ionic strength of the buffered aqueous solution. Invoking a nucleated supramolecular polymerization model that explicitly deals with the effects of screened Coulomb interactions, we correlate the degree of cooperativity of the supramolecular polymerization with the ionic strength of the solution, as probed by means of circular dichroism spectroscopy. Experiment and theory show that electrostatic interactions between the amphiphiles in the rods make the polymerization less cooperative, implying that the larger the concentration of mobile ions in the solution the larger the cooperativity due to their screening effect. We furthermore extract quantitative information about the effective surface charge densities of the supramolecular nanorods in solution, a parameter that has been particularly difficult to determine experimentally in other related self-assembled systems.

Tactoids of plate-like particles: size, shape, and director field.

We studied, by means of polarized light microscopy, the shape and director field of nematic tactoids as a function of their size in dispersions of colloidal gibbsite platelets in polar and apolar solvents. Because of the homeotropic anchoring of the platelets to the interface, we found large tactoids to be spherical with a radial director field, whereas small tactoids turn out to have an oblate shape and a homogeneous director field, in accordance with theoretical predictions. The transition from a radial to a homogeneous director field seems to proceed via two different routes depending in our case on the solvent. In one route, the what presumably is a hedgehog point defect in the center of the tactoid transforms into a ring defect with a radius that presumably goes to infinity with decreasing drop size. In the other route, the hedgehog defect is displaced from the center to the edge of the tactoid, where it becomes virtual again going to infinity with decreasing drop size. Furthermore, quantitative analysis of the tactoid properties provides us with useful information on the ratio of the splay elastic constant and the anchoring strength and the ratio of the anchoring strength and the surface tension.

Osmotic compression of droplets of hard rods: a computer simulation study.

By means of computer simulations, we study how droplets of hard, rodlike particles optimize their shape and internal structure under the influence of the osmotic compression caused by the presence of spherical particles that act as depletion agents. At sufficiently high osmotic pressures, the rods that make up the drops spontaneously align to turn them into uniaxial nematic liquid-crystalline droplets. The nematic droplets or "tactoids" that are formed this way are not spherical but elongated, resulting from the competition between the anisotropic surface tension and the elastic deformation of the director field. In agreement with recent theoretical predictions, we find that sufficiently small tactoids have a uniform director field, while large ones are characterized by a bipolar director field. From the shape and director-field transformation of the droplets, we are able to estimate the surface anchoring strength and an average of the elastic constants of the hard-rod nematic.

Influence of a random field on particle fractionation and solidification in liquid-crystal colloid mixtures.

The influence of a random-anisotropy (RA) type disorder on the phase separation of nematogen-colloid mixtures is studied theoretically by combining the phenomenological Landau-de Gennes, Carnahan-Starling, and hard-sphere crystal theories. We assume that the colloids enforce the RA disorder on the surrounding thermotropic liquid-crystal (LC) molecules. We adopt the Imry-Ma argument according to which the lower-temperature phase exhibits a domain-type pattern. The colloids impose a finite degree of orientational ordering even in the isotropic (paranematic) phase. In the ordered phase they give rise to a domain-type structure, resulting in the distorted nematic (speronematic) phase. The RA field opposes the phase separation tendency. With increasing disorder the difference between the paranematic and speronematic ordering decreases. Consequently there is a critical disorder, above which both phases become identical from the orientation point of view, but have different concentrations of colloids. We have also estimated another characteristic value of disorder above which the isotropic phase can exist only in a liquid state, the crystal phase being suppressed completely.

Isotropic-nematic interface and wetting in suspensions of colloidal platelets.

We study interfacial phenomena in a colloidal dispersion of sterically stabilized gibbsite platelets, exhibiting coexisting isotropic and nematic phases separated by a sharp horizontal interface. The nematic phase wets a vertical glass wall and polarized light micrographs reveal homeotropic surface anchoring both at the free isotropic-nematic interface and at the wall. On the basis of complete wetting of the wall by the nematic phase, as found in our density functional calculations and computer simulations, we analyze the balance between Frank elasticity and surface anchoring near the contact line. Because of weak surface anchoring, the director field in the capillary rise region is uniform. From the measured rise (6 microm) of the meniscus at the wall we determine the isotropic-nematic surface tension to be 3 nN/m, in quantitative agreement with our theoretical and simulation results.

Continuous director-field transformation of nematic tactoids.

We theoretically investigate the director field inside spindle-shaped nematic droplets, known as tactoids. Tactoids typically form in dispersions of rod-like colloidal particles. By optimising the bulk elastic and surface energies, we find that the director field crosses over smoothly from a homogeneous to a bipolar configuration with increasing droplet size, in a process that we postulate to involve two virtual point defects that move in from infinity towards the poles on the surface of the droplet. Our calculations show that these hypothesised virtual defects become true surface point defects or boojums only in the limit of infinite droplet volume, and that the more elongated the droplets are, the larger their volume has to be before a uniform director field distorts so as to become discernibly bipolar. The theory agrees well with available experimental data on the size dependence of the aspect ratio of tactoids.

Sex difference in target seeking behavior of developing cremaster muscles and the resulting first visible sign of somatic sexual differentiation in marsupial mammals.

Cremaster muscles are present in both male and female developing and adult marsupial mammals. They are complex structures and composed of several distinct bundles of striated muscle fibers provided with: (1) a distinct and extensive innervation; (2) a distinct blood vascular supply; (3) a distinct tendineous origin on the anterosuperior iliac spine; and (4) distinct target structures. The muscles thus seem to be separate anatomical entities and not a part of one or more of the layers of the ventral abdominal wall musculature. Cremaster muscles in males are elongated, are larger than in females, and for the most part are a component of the funiculus spermaticus. They insert on the distal part of the tunica vaginalis. The distal parts of the muscles in females are flattened ("fan shaped") and insert over a broad area on the dorsal borders of the mammary glands. Muscles in males have no relation whatsoever to the male mammary glandular rudiments. Muscles in females are attached at the base of the uterine round ligament. The remarkable sex difference in target structures of marsupial cremaster muscles becomes noticeable during perinatal life when outgrowing muscles take a different path in males and females. The initial appearance of this sexually dimorphic trait precedes the sexual differentiation of the genital ducts and external genitalia. In fetal males, the cremaster muscles grow in the direction of the site where scrotal bulges initially appear in the subcutaneous layers and later on the inguinal skin surface. They also take the gubernacular core of the ventral abdominal wall and the attached peritoneal epithelium with them during this outgrowth process. Consequently, this results in the development of a slitlike evagination of the abdominal lumen as the primary step to development of the processus vaginalis, while the testis and adjacent mesonephros and its duct are still attached to the posterior abdominal wall. In fetal females, the outgrowing cremaster muscles pass along the gubernacular core and, subsequently, this structure develops further as the tip (attached to the tubo-uterine junction) of the intra-abdominally protruding and further developing uterine round ligament. The female cremaster muscles grow further into caudal direction to shape a dorsal border of the developing mammary glands. The early onset of this sexually dimorphic outgrowth of cremaster muscles indicates that the "classical hormones" of sexual differentiation (anti-Müllerian hormone [AMH] and steroidal androgens) are not involved in this process. It could thus depend on primary genetic control with male development associated with the male-limited activity of genes on the Y-chromosomes and female development as the default process. Alternatively, the process in males could be under the control of an as yet unidentified third fetal testicular hormone involved in sexual differentiation processes which must then show an unexpectely early (i.e., perinatal) onset of its secretion.

Anti-müllerian hormone in relation to the growth and differentiation of the gubernacular primordia in mice.

The present study analysed gubernaculum development in mice that had been induced, through transgenesis, to express human anti-Müllerian hormone (h-AMH) throughout prenatal life. Growth and differentiation of the gubernacular primordia were assessed through the analysis of serial, transverse or sagittal, histological sections of the lower abdomen. Transgenic males and females expressed biologically active amounts of h-AMH as measured by sensitive and specific ELISA and evidenced through the regression, in females, of Müllerian ducts after day 13 of prenatal life. Gubernacular primordia became distinguishable at the same age in control and transgenic male and female fetuses on day 12 after coitus. In both groups gubernacular cords (inguinal folds of the genital mesenteries) increased in length more in females than in males while gubernacular cones showed larger growth in males. h-AMH thus appeared not to affect the sexually dimorphic pattern of growth and development of these structures. Growth and differentiation of the gubernacular primordia was further examined in 18-day-old control and h-AMH transgenic fetuses that had been exposed to testosterone propionate injected into their mothers on days 12 and 14 of pregnancy. Testosterone treatment affected, to a minor extent, the growth of the female gubernacular cords: these were reduced in length (but had a larger surface area) compared with controls. The gubernacular cones were slightly increased in length but male-like differentiation of the tissues of the cones into a muscular and mesenchymal component was not noticed to any extent. The observations thus add experimental support to the contention that AMH, even in combination with testosterone, is not effective in establishing the male pattern of gubernacular primordia development.

Development, structure and function of the cranial suspensory ligaments of the mammalian gonads in a cross-species perspective; their possible role in effecting disturbed testicular descent.

The present review aims to present a perspectiveon a relatively unknown part of the mammalian internal genitalia: their cranial suspensory apparatus. This apparatus shows wide divergence of development when examined during the fetal period or during adulthood, in males or females, or in individuals across a variety of species. In rats and other mamalian species the apparatus undergoes a distinct patern of sexually dimorphic development and fetal testicular androgens are proposed to play a key role in this process. Extensive development of this suspensory apparatus in females is argued to be a part of the anatomical adaptations of the genital apparatus to support the internal genitalia throughout pregnancy, including the relatively enormous growth towards the time of parturition. Minor development of this apparatus in males is judged to be a part of the anatomical requirements allowing developing testes to become displaced from the dorsal abdominal wall during the first stage of testicular descent. Extensive development of this suspensory apparatus in males generally seems to hinder testicular descent. Accordingly, the apparatus is well developed in so-called testicond species which do not show testis descent as a part of their normal male genital development. Furthermore, arguments are adduced that inappropriate and extensive development in species with testis descent may be a key aetiological factor in the disturbance of this process. Diagnosis and treatment of human cryptorchidism might profit from including an analysis of the development and function of (remnants of) the cranial testicular and epididymal suspensory apparatus.

Towards a rational terminology in the study of the gubernaculum testis: arguments in support of the notion that the cremasteric sac should be considered the gubernaculum in postnatal rats and other mammals.

There is need for a consistent definition of structures caudal to the testis that variously are termed 'gubernaculum testis' as a basis for understanding the emergence and sexually dimorphic further growth and differentiation of this specifically mammalian structure. Rodent fetuses undergo a stage of development during which there is almost complete unanimity as to the definition of the 'gubernaculum' as a papilla-like structure (often called conus inguinalis) protruding from the area of the internal inguinal ring. This structure shows at least 3 readily distinguishable components before birth. Postnatally, the papilla-like gubernaculum starts to undergo inversion to become the tunica of the sac-like processus vaginalis. The 3 components of the fetal gubernaculum develop further uninterruptedly, but with a different spatial arrangement, as parts of the wall of a sac rather than as parts of a papilla-like structure. Comparison of this process in rodents with that in other mammals (pig, horse, man) revealed an essentially identical emergence of a papilla-shaped gubernaculum with similar constituents. Initial development of the processus vaginalis also began with the inversion of the gubernacular papilla. Cattle fetuses appeared exceptional as outgrowth of the processus vaginalis occurred without a preceding papilla-shaped gubernaculum in the area of the inner inguinal ring. The findings lead to the following conclusions. (1) In rodents, the whole of the postnatally developing processus vaginalis, including therefore its cremasteric muscles but without the attached genital mesentery, is to be viewed as the male postnatal gubernaculum. Sexual differentiation of the gubernacular primordia includes a sex-specific effect on the morphogenesis of all constituents of the processus vaginalis sac including cremasteric muscle cells. (2) Gubernacular growth and differentiation appear essentially a uniform process throughout the placentalia mammalian class; only quantitative differences occur in the extent of initial development of an intra-abdominal conus inguinalis and later cremaster muscles.

Bilateral cryptorchidism in a dog with persistent cranial testis suspensory ligaments and inverted gubernacula: report of a case with implications for understanding normal and aberrant testis descent.

The genital system of a dog with bilateral intra-abdominal testes is described. External virilisation was normal except for an empty scrotum. Internally there was a prostate of normal macroscopic and histological appearances and, bilaterally, a fully developed male genital tract. Testicular vasculature was normal. Cranial to each testis, there was a strong ligament lying at the free edge of the gonadal/genital mesentery and running between the cranial tip of the testis/epididymis and the area craniolateral of the ipsilateral kidney. It was impossible to push the testes into the inguinal canal because of this strong ligament. Caudal to each testis, there was an elongated whitish structure between the caudal pole of the epididymis and the area of the internal inguinal ring. On closer inspection this structure appeared to be the inverted and elongated processus vaginalis sac. There was a minor ligament at the free border of the inguinal fold of the genital mesentery between the tip of this inverted processus vaginalis and the adjacent junction of the cauda epididymidis and vas deferens. The findings suggest that persistence of the fetal cranial gonadal suspensory ligaments could have been the major aetiological factor in this case of cryptorchidism. Their persistence could have prevented caudal outgrowth of the processus vaginalis with its consequent development into an intra-abdominal papilla-like structure. Inappropriate persistence of the cranial suspensory ligaments in male rodents, pig, and cattle has been associated with insufficient exposure of their primordia to androgen during fetal life. It is uncertain whether a similar deficiency could underlie persistence of these structures in the present specimen. The findings add further weight to the hypothesis that regression of the cranial gonadal suspensory ligament in males is a key event in the process of testis descent. The human homologue of this ligament deserves more attention in the analysis and treatment of human cryptorchidism.

Foetal genital development in Hyrax capensis, a species with primary testicondia: proposal for the evolution of Hunter's gubernaculum.

BACKGROUND: Control of testicular descent is poorly understood. There are a number of mammalian species in which testis descent does not occur, and the phenomenon is called testicondia. Analysis of foetal development of such species could contribute to a better understanding of the key events in anatomical development underlying testis descent. Specific attention is to be given to the development of the so-called gubernaculum of Hunter: a structure of complex architecture and composition, which extends from the caudal pole of the mesonephric remnants into the inguinal abdominal wall and which is present in most mammals but not in submammalian vertebrates. METHODS: Serially sectioned male and female foetuses of Hyrax capensis, a species in which testes remain close to the caudal pole of the kidneys throughout life, were analysed for architecture of the developing genital apparatus and the immediately surrounding structures. The results of this analysis were compared with those from a similar analysis of reptiles, of monotremata without testis descent, and of mammals with testis descent. RESULTS: Reptiles and Monotremata showed no gubernacular structures. Mammals with testis descent showed gubernacular growth and differentiation which varied between the sexes and with the stage of foetal development. Hyrax capensis foetuses showed the development of only one component of the gubernaculum: the gubernacular cord as a part of the mesonephric mesentery and extending between the caudal pole of the mesonephros (or mesonephric remnants in older foetuses) and the lateral bladder ligament. No part developed in the inguinal abdominal wall components, which are the primordia of the cremaster sacs in species with testis descent. CONCLUSION: Hyrax capensis shows only partial development of the gubernacular structures, and, specifically, the primordia of the cremaster sacs remain absent. Thus, this species lacks a key anatomical condition for testis descent. Gubernacular architecture in Hyrax capensis seems of a degree intermediate between egg laying monotremata mammals and mammals with testis descent. A model is proposed within which to understand the development of the gubernacular components within the mammalian class.

Human (and some other primates') uterine teres ligament represents a mammalian developmental novelty.

BACKGROUND: The primordia of the structures developing into the mammalian male cremaster sacs emerge as well in females fetuses. In most species the structures developing from these primordia in females remain inconspicuous: the so-called uterine teres ligament consisting of a slender part across the uterine broad ligament and a more or less developed bulbous structure at the site where this ligament inserts into the inguinal abdominal bottom. Not many data are available concerning the growth, development, or function of the uterine teres ligament. In humans--and also in other "higher" female primates--the uterine teres ligament is a major structure consisting mainly of smooth musculature. It is attached to the ventral aspect of the tubo-uterine junction. From there it courses across the uterine broad ligament and extends, retroperitoneally, to the inguinal region where it pierces through the inguinal canal to end in the tissues ventral of the pubic bones. OBSERVATIONS: Analysis of the fetal development of the human uterine teres ligament, as compared with that of various other non-primate mammals, offers an explanation for its unusual anatomical condition. Evidence is conferred that, in human fetuses, there is no counterpart for the slender ligament across the broad ligament in other mammals. Instead, the homologue of the rudimentary bulbous structure in the abdominal bottom of non-primate females develops into a strong muscular structure which is directly connected to the (para-)menonephric duct wall. CONCLUSION: It is concluded that the human uterine teres ligament is to be judged a structure different from that of other, non-primate, mammals. It is speculated that the unusual structure of the human teres ligament is related to one or more of the many unusual features of human uterine development: as a single organ (uterus simplex), with a position deep in the abdominal cavity below the pelvic brim, and far away from the posterior abdominal wall. The unusual anatomical position may require an unusual construction of the uterine suspensory apparatus of which the teres ligament is one component.

Studies on the role of TRH and corticosterone in the regulation of prolactin and thyrotrophin secretion during lactation.

This study describes the effects of litter size and acute suckling on the synthesis and release of hypothalamic TRH, as indirectly estimated by determination of hypothalamic prothyrotrophin-releasing hormone (proTRH) mRNA and median eminence TRH content. The effects of litter size (five or ten pups) were studied throughout lactation, while suckling-induced acute changes were analyzed on day 13 of lactation in dams with ten pups. In view of the enhanced adrenal activity during lactation and recent evidence that corticosteroids have negative effects on hypothalamic TRH, we also studied adrenalectomized (ADX) dams treated with corticosterone to maintain basal plasma corticosterone levels. In addition to an increased plasma level of prolactin (PRL), adrenal weight and plasma corticosterone increased, while plasma TSH, tri-iodothyronine (T3), thyroxine (T4) and free T4 (FT4) levels decreased during lactation. Litter size correlated positively with plasma PRL, adrenal weight and plasma corticosterone. No effect of litter size was observed on plasma T3, but rats with ten pups had lower plasma TSH, T4 and FT4 than rats with a five-pup litter. Compared with dioestrous rats, lactating rats showed an increased hypothalamic proTRH mRNA content on day 2, but not on days 8 and 15 of lactation. Median eminence TRH in lactating rats gradually increased until day 15 and decreased thereafter. Acute suckling, after a 6-h separation of mother and pups, rapidly increased plasma PRL and corticosterone in the mothers, but had no effects on plasma TSH and thyroid hormone levels. Hypothalamic proTRH mRNA increased twofold after 0.5 h of suckling, and then gradually returned to presuckling values after 6 h. Compared with sham-operated rats, corticosterone-substituted ADX rats with ten pups had increased plasma PRL and TSH, hypothalamic proTRH mRNA and pituitary TSH beta mRNA on day 15 of lactation. Moreover, while acute suckling did not enhance TSH release in sham-operated rats, it provoked not only PRL but also TSH release in corticosterone-substituted ADX dams. It is concluded that suckling exerts a rapid, positive effect on hypothalamic proTRH mRNA content. However, the concurrent enhanced adrenal activity has negative effects on hypothalamic proTRH gene expression resulting in a suppressed hypophysial-thyroid axis during lactation. While TRH appears to play a role in PRL release during the first days of lactation and during acute suckling, TRH seems not important in maintaining PRL secretion during continued suckling.