Clinical Study of a Physician Modified Y-Type Iliac Branch Device (PMYIBD) in the Endovascular Repair of Abdominal Aortic Aneurysms to Preserve the Internal Iliac Artery.

OBJECTIVES: To report the method and curative effect of using a physician modified Y-type iliac branch device (PMYIBD) to preserve the internal iliac artery during the endovascular repair of abdominal aortic aneurysms. METHODS: From September 2018 to April 2022, 24 patients with abdominal aortic aneurysms or dissecting aneurysms, including 19 true aneurysms and 5 dissecting aneurysms involving the common iliac artery were treated in our department. The average age was (65.3 ± 7.6) years. All patients underwent preoperative evaluation by enhanced computed tomography. Combined with intraoperative angiography, a Y-type stent graft was prepared during surgery to perform endovascular repair of abdominal aortic aneurysms. RESULTS: All operations were successfully completed. The average operative duration was (224.8 ± 44.1) minutes. A total of 24 internal iliac arteries were reconstructed. The average follow-up time was (27.1 ± 13.5) months. During the follow-up, there was no expansion of aneurysm cavity, no endoleak or stent displacement, and no death occurred in all patients. DISCUSSION: The physician-modified Y-type iliac branched device (PMYIBD) provides an effective method for full-cavity repair. It has a wide range of indications and convenience. According to follow-up results, the early and mid-term had good curative effects; however, the long-term effects require further follow-up. CONCLUSION: The modified Y-type IBD technique is safe and effective for aortic diseases involving internal iliac artery especially with complex anatomy. CLINICAL IMPACT: It is meaningful to preserve the IIA during EVAR. The use of PMYIBD provides a simple and effective method for the total endovascular repair of aortic diseases involving the IIA. Several advantages such as minimal trauma, low mortality, low complication rates and perfect short- and medium-term effects emerge in clinical practice. PMYIBDs are good choices for clinicians before suitable commercial stents are available in markets.

Risk factors for target vessel endoleaks after physician-modified fenestrated or branched endovascular aortic arch repair: A retrospective study.

Objective: Fenestrated or branched endovascular aortic arch repair (fb-arch repair) is an effective option for treating complex aortic arch lesions, including thoracic aortic aneurysms and aortic dissections. However, the relatively high rate of re-intervention due to target vessel (TV)-related endoleaks have raised concerns. This study aimed to determine risk factors for TV-related endoleaks after fb-arch repair. Methods: This was a retrospective analysis of all patients undergoing fb-arch repair between 2017 and 2021in nanjing drum tower hospital of China. All the patients underwent computed tomography angiography (CTA) before surgery; at discharge; and at 3 months, 6 months, and yearly post-discharge. All procedures are performed with physician modified grafts. Two experienced vascular surgeons used CTA and vascular angiography data to assess endoleaks. The study endpoints were mortality, aneurysm rupture, and emergence of and re-intervention for TV-related endoleaks. Results: During the follow-up period, 218 patients underwent fb-arch repair. There were seven perioperative deaths and four deaths during follow-up (two myocardial infarctions and two malignancies). There were nine additional patients who were excluded from the study (two strokes, three with abnormal aortic arch anatomy, and four with insufficient clinical data). Among the 198 patients considered (mean age, 59 ± 13.3 years; 85% male), 309 branch arteries were revascularized. A total of 35 TV-related endoleaks were identified in 28 patients during a mean follow-up of 23 ± 14 months (median 23, IQR 26.3): six type Ic, 4 type IIIb, and 20 type IIIc endoleaks. Patients in the endoleak group had greater aortic arch segment diameters (43.1 ± 5.1 vs. 40.3 ± 4.7; P = 0.004) and a greater number of TVs revascularized (2.0 ± 0.8 vs. 1.5 ± 0.8; P = 0.004) than those in the non-endoleak group. However, the morphological classification of the aortic arch did not seem to affect the occurrence of TV endoleaks (13%, 14%, and 15% for type І, II, and III aortic arches, respectively; P = 0.957). Pre-sewing branch stents in the fenestration position reduced the risk of TV endoleaks (5% vs. 14%; P = 0.037). Additionally, in TVs affected by aortic aneurysm or dissection, the risk of endoleaks increased after reconstruction (17% vs. 8%; P = 0.018). The incidence of secondary TV-related endoleaks after fb-arch repair was 14.1%. Conclusion: The data from this study showed that the incidence of secondary target vessel related endoleaks after fb-arch repair is approximately 14.1%. Additionally, patients with a larger aortic arch diameter or more revascularized arteries during surgery were at increased risk TV-related endoleaks. The target vessels originating from the false lumen or aneurysm sac are more prone to endoleaks after reconstruction. Finally, prefabricated branch stents reduced risk of TV-related endoleaks.

Three-Dimensional Printing to Guide Fenestrated/Branched TEVAR in Triple Aortic Arch Branch Reconstruction With a Curative Effect Analysis.

PURPOSE: To summarize experience with and the efficacy of fenestrated/branched thoracic endovascular repair (F/B-TEVAR) using physician-modified stent-grafts (PMSGs) under 3D printing guidance in triple aortic arch branch reconstruction. MATERIALS AND METHODS: From February 2018 to April 2022, 14 cases of aortic arch aneurysms and 30 cases of aortic arch dissection (22 acute aortic arch dissection and 8 long-term aortic arch dissection)were treated by F/B-TEVAR in our department, including 34 males and 10 females, with an average age of 59.84 ± 11.72 years. Three aortic arch branches were affected in all patients. A 3D-printed model was made according to computed tomography angiography images and used to guide the fabrication of PMSGs. All patients were followed up. RESULTS: A total of 132 branches were successfully reconstructed with no case of conversion to open surgery. The average operation time was 4.97 ± 1.40 hours, including a mean 44.05 ± 7.72 minutes for stent-graft customization, the mean postoperative hospitalization duration was 9.91 ± 4.47 days, the average intraoperative blood loss was 480.91 mL (100-2810 mL), and the mean postoperative intensive care unit monitoring duration was 1.02 days (0-5 days). No deaths occurred within 30 days of surgery. Postoperative neurological complications occurred in 1 case (2.3%), and retrograde type A dissection occurred in 1 case (2.3%). CONCLUSION: Compared with conventional surgery, triple aortic arch branch reconstruction under the guidance of 3D printing is a minimally invasive treatment method with the advantages of accurate positioning, rapid postoperative recovery, few complications, and reliable short- to mid-term effects. CLINICAL IMPACT: At present the PMSG usually depend on imaging data and software calculation. With the guidance of 3D printing technology, image data could be transformed into 3D model, which has improved the accuracy of the positioning of the fenestrations. The diameter reduction technique and the internal mini cuff technique have made a complement to the slimed-down fenestration selection process and the low rate of endoleak. As reproducible study, our results may provide reference for TEVAR in different cases.

Mechanisms of grazing management impact on preferential water flow and infiltration patterns in a semi-arid grassland in northern China.

Grazing management is widely used to control grassland degradation in Inner Mongolia. However, the correlation between the soil physical properties, root traits, and infiltration patterns of different types of grazing management has seldom been studied. To reveal the effect of grazing management on water infiltration and preferential flow behavior, we first investigated the soil and plant properties in a grazing exclusion (19 years, GE), cold-season grazing (19 years, CG), and free-grazing grassland (19 years, FG) in a semi-arid grassland in Inner Mongolia. Dye tracer infiltration was adopted to obtain the water infiltration patterns from different types of grazing management. Finally, root biomass and root morphological traits were measured in a field experiment. The results showed that the plant height, vegetation coverage, richness index, Shannon-Wiener index, soil water content, total porosity, and mean weight diameter were higher at the GE site than at the FG site, whereas soil bulk density and sand content were lower at the GE site than at the FG site (P < 0.05). In addition, the root mean diameter, specific root length, and root mass density were higher at the GE site than at the FG site. As a result, differences in these root traits and soil and vegetation properties affected the preferential water flow behavior in the three types of grassland. The preferential flow evaluation index (PFI) of the GE, CG, and FG sites was 0.89, 0.30, and 0.15, respectively, which indicated that more obvious preferential flow occurred at the GE site than at the CG and FG sites. These findings highlight that the long-term GE enhanced plant density and root biomass, which could potentially promote the natural restoration of soil pores and preferential water infiltration. Therefore, local governments and herders should implement GE rather than other grazing management practices to prevent grassland degradation.

Polylactic acid/polyvinyl alcohol-quaternary ammonium chitosan double-layer films doped with novel antimicrobial agent CuO@ZIF-8 NPs for fruit preservation.

ZIF-8, a subclass of metal organic frameworks (MOFs), was employed as the CuO carriers because of its high surface areas and good dispersibility. A novel antibacterial agent CuO@ZIF-8 was synthesized by environmentally-friendly direct calcination strategy, and introduced into the composite double-layer films for packing materials. The double-layer films were prepared via solution casting method with polylactic acid (PLA) and polyvinyl alcohol (PVA)-quaternary ammonium chitosan as the matrix of outer layer and inner layer, respectively; and CuO@ZIF-8 nanoparticles were introduced into the PVA-quaternary ammonium chitosan layer. The double-layer films exhibited superior antibacterial activity resulted from the uniform dispersion of CuO by ZIF-8 carriers. The elongation at break was enhanced and up to 17.13%, about 2.4-fold that of PLA films. Meanwhile, the films provided low water vapor permeability and strong UV-barrier ability which were attributed to the lay-by-layer casting, CuO@ZIF-8 doping and TiO2 addition. Cherry tomato preservation experiment revealed that the composite films retarded the growth of harmful microorganisms on the fruit surface. MTT assay confirmed the cytocompatibility of the films. The easily fabricated double-layer films presented potential possibility in the field of biodegradable food packaging.

Molecular Etiology in Thumb Polydactyly in Mutated GLI3 Mouse Gene.

Sporadic thumb polydactyly with nonfamily inheritance is the most common in clinical work. This study focused on characterization of GLI3 gene function. We constructed the plasmid with p.m948i point mutation of GLI3 and transfected it into mouse embryonic fibroblasts (MEFs) to study the effects and potential mechanism of the mutant gene. The RNA of GLI3 mutant cells was extracted and analyzed by transcriptome sequencing and bioinformatics. Finally, we constructed cbx3 overexpression plasmid, designed siRNA for gene silencing, and transfected it into the MEFs. Cell proliferation and invasion ability of the MEFs were examined. The results showed that there were 2,452 differential expression genes in the MEFs transfected with GLI3 mutant plasmid compared with wild-type MEFs. The results of differential expression analysis showed that the cbx3 gene was significantly up-regulated. Overexpression of cbx3 in MEFs promoted cell proliferation and invasion, while siRNA knockdown of cbx3 expression reduced proliferation and invasion. GLI3 gene mutation in MEFs resulted in cbx3 up-regulation and promoted MEF proliferation and invasion. This study further clarified the potential function of GLI3 in limb development, established a new relationship between gene mutation and polydactyly, and preliminarily clarified the possible signal pathway, all of which have laid a foundation for further study on the etiology of polydactyl.

Dual stimuli-responsive polypeptide-calcium phosphate hybrid nanoparticles for co-delivery of multiple drugs in cancer therapy.

In this study, a new type of polypeptide, crosslinked methoxy poly(ethylene glycol)-g-poly(aspartic acid)-g-tyrosine (CPPT), was synthesized via a green and simple one-pot polymerization method. With the disulfide-crosslinked interlayer and the CaP shell, the pH and redox dual-sensitive polypeptide-based organic-inorganic hybrid nanoparticles encapsulated curcumin (Cur) into the hydrophobic core of micelles and loaded doxorubicin hydrochloride (DOX) on the hydrophilic segment of micelles as well as CaP shell. The spherical Cur- and DOX-loaded nanoparticles (CPPT@CaP-CD) showed a hydrodynamics size of about 157.9 ± 3.9 nm. The premature leakage of drugs from the nanoparticles at physiological pH was efficiently restrained because of the enhanced structure integrity, whereas at acidic and hypoxia microenvironment the release of both drugs was promoted due to the rapid dissolution of the CaP shell and the break of the disulfide crosslinked network, facilitating the stimuli-responsive controllable drugs release. In vitro anticancer activity evaluation revealed that the co-loaded nanoparticles presented higher cytotoxicity against A549 cells compared with that of the free combination of Cur + DOX. Confocal laser scanning microscopy observation indicated that more DOX and Cur were released into the nucleus triggered by the up-regulated intracellular glutathione (GSH) concentration and decreased pH, displaying enhanced cell uptake. The self-assembling polypeptide-based dual-sensitive drug co-delivery system could be a promising platform for efficient chemotherapy.

Poly(aspartic acid)-based pH-responsive targeting co-delivery nanoparticles.

Encapsulation of therapeutic molecules into nanocarrier is an extensively explored strategy to treat cancer more effectively. In this study, pH-responsive targeting dual-agent delivery nanoparticles were prepared, into which hydrophilic doxorubicin hydrochloride (DOX) and hydrophobic curcumin (CUR) were entrapped. Tyrosine (Tyr) was grafted onto poly(aspartic acid) (PASP) to produce PASP-Tyr, the following reaction between hyaluronic acid (HA) and ethylenediamine (EDA) modified PASP-Tyr formed the nanocarrier HA-EDA-PASP-Tyr (HEPT), and the loading capacity was up to 50.9 ± 4.3% for CUR and 26.0 ± 1.9% for DOX. The spherical HEPT with the mean particle size of 142.9 ± 11.4 nm expanded and deformed into petaloid pattern with an increased size of about 2 µm when triggered by the acidic microenvironment. In vitro anticancer activity evaluation revealed that the co-loaded (DOX+CUR)@HEPT nanoparticles presented higher cytotoxicity against HCT-116 cells compared with that of the free combination of (DOX+CUR). Confocal laser scanning microscopy observation indicated that HEPT carrier promoted cellular uptake of drugs by means of active targeting capacity of HA ligand. With high loading capacity and tailored carrier structure, the nanoparticles formulations may offer a new strategy for cancer treatment.

Clinical potential of miRNA-221 as a novel prognostic biomarker for hepatocellular carcinoma.

miRNA-221 is one of the over 700 kinds of currently known microRNAs (miRNAs) and is up-regulated in multiple tumors, suggesting that it may be a potential carcinogenic miRNA. Few studies have explored the relationship between miRNA-221 and hepatocellular carcinoma (HCC). We performed real-time quantitative polymerase chain reaction (qPCR) to detect miRNA-221 expression in HCC and para-carcinoma tissues and to explore the relationship between abnormal expression of miRNA-221 and clinicopathological features of HCC patients. miRNA-221 expression was significantly higher in HCC tissues than in adjacent tissues (P < 0.001). We analyzed the relationship between miRNA-221 expression level and clinicopathological characteristics of HCC patients. Our results suggested that miRNA-221 expression level was closely related to tumor stage (P = 0.012), number of tumor nodes (P = 0.018), and microvascular invasion (P = 0.010) in HCC patients. The results of survival analysis suggested that HCC patients with up-regulated miRNA-221 expression had a shorter survival time. The high miRNA-221 expression indicates the poor prognosis of HCC patients; thus, miRNA-221 can be regarded an important molecular marker for HCC prognosis.

Nanoparticle enlarged interfacial effect on phase transition of 1-octadecanol/silica composites.

Motivated by the interest in an interfacial effect on crystallization behaviors and material properties of polymer nanocomposites, phase behaviors of a novel model system for polymer nanocomposite, 1-octadecanol/silica nanosphere composites (C18OH/SiO2), were studied by means of thermal analysis and wide-angle X-ray diffraction. Although a huge specific surface area of silica nanoparticles enlarges the surface-volume ratio of C18OH molecules, surface freezing phenomenon is not observed by DSC in the C18OH/SiO2 composites. While pure C18OH exhibits rotator RIV phase with molecules tilted with respect to the layer normal, the silica network favors and enhances untitled RII phase by disturbing the layering arrangement. Moreover, the confined C18OH shows a polycrystalline mixture of orthorhombic ß form and monoclinic γ form. It is demonstrated that the interfacial interaction between the C18OH molecules and the silica surface contributes to the peculiar phase transition behaviors of C18OH/SiO2 composites. The investigation of the model system of long-chain alcohol/nano-SiO2 composites may help us to understand the complicated interfacial effect on phase behaviors and material properties of polymer nanocomposite systems.

Confined phase diagram of binary n-alkane mixtures within three-dimensional microcapsules.

The confined phase behaviors of microencapsulated normal hexadecane/octadecane mixtures (abbreviated as m-C16/C18) have been investigated by combination of differential scanning calorimetry and in situ wide-angle X-ray scattering. The binary alkane mixtures confined in three-dimensional geometrical space demonstrate two novel crystallization features. The surface freezing is significantly enhanced after C16/C18 mixtures being encapsulated, and the surface monolayer formed is proved to be an ideal solid solution composed by C16 and C18. Furthermore, m-C16/C18 mixtures are trapped into a stabilized rotator phase below the crystallization temperatures, whereas C16/C18 mixtures with certain compositions form the low-temperature crystalline structure directly. These confined crystallization features originate from the jointed effects of spatial confinement and chain mixing of the components. Moreover, the phase diagram of the confined binary alkane mixtures (m-C16/C18) is successfully established for the first time, which enlightens the crystallization features of other spatially confined soft-matter binary systems.

Crystallization features of normal alkanes in confined geometry.

How polymers crystallize can greatly affect their thermal and mechanical properties, which influence the practical applications of these materials. Polymeric materials, such as block copolymers, graft polymers, and polymer blends, have complex molecular structures. Due to the multiple hierarchical structures and different size domains in polymer systems, confined hard environments for polymer crystallization exist widely in these materials. The confined geometry is closely related to both the phase metastability and lifetime of polymer. This affects the phase miscibility, microphase separation, and crystallization behaviors and determines both the performance of polymer materials and how easily these materials can be processed. Furthermore, the size effect of metastable states needs to be clarified in polymers. However, scientists find it difficult to propose a quantitative formula to describe the transition dynamics of metastable states in these complex systems. Normal alkanes [CnH2n+2, n-alkanes], especially linear saturated hydrocarbons, can provide a well-defined model system for studying the complex crystallization behaviors of polymer materials, surfactants, and lipids. Therefore, a deeper investigation of normal alkane phase behavior in confinement will help scientists to understand the crystalline phase transition and ultimate properties of many polymeric materials, especially polyolefins. In this Account, we provide an in-depth look at the research concerning the confined crystallization behavior of n-alkanes and binary mixtures in microcapsules by our laboratory and others. Since 2006, our group has developed a technique for synthesizing nearly monodispersed n-alkane containing microcapsules with controllable size and surface porous morphology. We applied an in situ polymerization method, using melamine-formaldehyde resin as shell material and nonionic surfactants as emulsifiers. The solid shell of microcapsules can provide a stable three-dimensional (3-D) confining environment. We have studied multiple parameters of these microencapsulated n-alkanes, including surface freezing, metastability of the rotator phase, and the phase separation behaviors of n-alkane mixtures using differential scanning calorimetry (DSC), temperature-dependent X-ray diffraction (XRD), and variable-temperature solid-state nuclear magnetic resonance (NMR). Our investigations revealed new direct evidence for the existence of surface freezing in microencapsulated n-alkanes. By examining the differences among chain packing and nucleation kinetics between bulk alkane solid solutions and their microencapsulated counterparts, we also discovered a mechanism responsible for the formation of a new metastable bulk phase. In addition, we found that confinement suppresses lamellar ordering and longitudinal diffusion, which play an important role in stabilizing the binary n-alkane solid solution in microcapsules. Our work also provided new insights into the phase separation of other mixed system, such as waxes, lipids, and polymer blends in confined geometry. These works provide a profound understanding of the relationship between molecular structure and material properties in the context of crystallization and therefore advance our ability to improve applications incorporating polymeric and molecular materials.

Phase transition behavior of a series of even n-alkane C(n)/C(n+2) mixtures confined in microcapsules: from total miscibility to phase separation determined by confinement geometry and repulsion energy.

The phase behaviors of binary consecutive even normal alkane (n-alkane) mixtures (n-C(n)H(2n+2)/n-C(n+2)H(2n+6), with mass ratios of 90/10 and 10/90) with different average carbon numbers n¯ both in the bulk state (abbreviated as C(n)/C(n+2)) and in nearly monodisperse microcapsules (abbreviated as m-C(n)/C(n+2)), have been investigated by the combination of differential scanning calorimetry and temperature-dependent X-ray diffraction. The phase behavior of n-alkane mixtures gradually shifts from complete phase separation, partial miscibility to total miscibility in both bulk and microcapsules with the increase of average carbon numbers n¯. There are critical points for average carbon numbers of C(n)/C(n+2), where the corresponding mixtures exhibit coexistence of a triclinic phase (formed by alkane with a longer chain) and an orthorhombic ordered phase (formed by the two components of mixtures). Due to the confinement from hard shells of microcapsules, the critical points of m-C(n)/C(n+2) are smaller than those of C(n)/C(n+2). Such a phase behavior originates from the delicate combined action of confinement and repulsion energy for the encapsulated n-alkane mixtures with different average carbon numbers n¯. When n¯ is less than the critical point, the repulsion energy between the two kinds of molecules exceeds the suppression effect of confinement, and phase separation occurs in microcapsules. It is believed that the average carbon number is another important factor that exerts strong negative influence on the phase separation of m-C(n)/C(n+2) systems.

Confined crystallization of n-hexadecane located inside microcapsules or outside submicrometer silica nanospheres: a comparison study.

Crystallization and phase transition behaviors of n-hexadecane (n-C16H34, abbreviated as C16) confined in microcapsules and n-alkane/SiO2 nanosphere composites have been investigated by the combination of differential scanning calorimetry (DSC) and temperature-dependent X-ray diffraction (XRD). As evident from the DSC measurement, the surface freezing phenomenon of C16 is enhanced in both the microcapsules and SiO2 nanosphere composites because the surface-to-volume ratio is dramatically enlarged in both kinds of confinement. It is revealed from the XRD results that the novel solid-solid phase transition is observed only in the microencapsulated C16, which crystallizes into a stable triclinic phase via a mestastable rotator phase (RI). For the C16/SiO2 composite, however, no novel rotator phase emerges during the cooling process, and C16 crystallizes into a stable triclinic phase directly from the liquid state. Heterogeneous nucleation induced by the surface freezing phase is dominant in the microencapsulated sample and contributes to the emergence of the novel rotator phase, whereas heterogeneous nucleation induced by foreign crystallization nuclei dominates the C16/SiO2 composite, leading to phase transition behaviors similar to those of bulk C16.

Binary n-alkane mixtures from total miscibility to phase separation in microcapsules: enrichment of shorter component in surface freezing and enhanced stability of rotator phases.

The crystallization behaviors of binary normal alkane (n-alkane) mixtures with a series of carbon number difference (denoted as Δn), both in the bulk state and in nearly monodisperse microcapsules, have been investigated by the combination of differential scanning calorimetry (DSC) and temperature-dependent X-ray diffraction (XRD). As revealed by the DSC data, the surface freezing temperature (denoted as T(s)) of spatially confined binary n-alkane mixtures with large Δn is lower than the calculated value due to the enrichment of shorter component in the surface freezing phase. More alkane molecules with shorter carbon chain are located on the interface between the inner shell of microcapsules and the bulk mixture, thus leading to the decrease of the average chain length of the surface freezing phase and corresponding lower T(s). Furthermore, XRD results have proved that the enhanced surface freezing phenomenon can contribute to the stabilization of the rotator phases in n-alkane mixtures and even induce the crossover of some certain rotator phase (RII) from transient to metastable. However, the decisive reason for such stabilization or crossover is attributed to the suppression of the orienting movement of alkane molecules toward their next-nearest neighbors within the layer of rotator phases.

Confined crystallization of binary n-alkane mixtures: stabilization of a new rotator phase by enhanced surface freezing and weakened intermolecular interactions.

The present work reports the confined crystallization behaviours of binary even-even normal alkane (n-alkane) mixtures of n-octadecane (n-C(18)H(38)) and n-eicosane (n-C(20)H(42)), which are microencapsulated in monodisperse microcapsules, using the combination of differential scanning calorimetry (DSC) and temperature-dependent X-ray diffraction (XRD). A new metastable rotator phase (RII) absent in the bulk state, has been detected for the n-alkane mixture in confined geometry under all the investigated compositions. Such a crossover is attributed to the lower interfacial energy due to the same in-planar hexagonal structure of the surface monolayer and RII, as well as the weakened intermolecular interaction in alkane mixtures. This is the first time that RII is found in such a binary even-even n-alkane mixture that neither of the components contains RII phase in the crystallization process. Furthermore, based on the variation of alkane molecule conformation and in-planar structure with temperature, the correlations between the phase transition temperature and composition have been discussed.

Crystallization behavior of binary even-even n-alkane mixtures in microcapsules: effect of composition and confined geometry on solid-solid phase separation.

The crystallization behaviors of binary even-even normal alkane (n-alkane) mixtures (n-C(18)H(38)/n-C(20)H(42), abbreviated as C(18)/C(20)) with different compositions, both in the bulk state and in nearly monodisperse microcapsules, have been investigated by the combination of differential scanning calorimetry and temperature-dependent X-ray diffraction. The solid-solid phase separation, usually observed during the cooling process of bulk samples, is greatly suppressed and even eliminated after being microencapsulated, with the orthorhombic-ordered phase dominating in the low-temperature crystal. Such a crystallization transition is attributed to the special interaction between the two even n-alkanes and the confined environment in microcapsules. The triclinic ordered phase, solely formed by the single even n-alkanes (C(18) or C(20)), becomes less stable due to the weakening of the layered structure and the suppression of the terminal methyl-methyl interactions in the confined geometry, which favors the miscibility of the two components. Furthermore, besides the chain-length difference and the composition, the confined environment is proved to be another important factor to exert strong positive influence on suppressing the solid-solid phase separation of C(18)/C(20) binary system.

Phase change materials of n-alkane-containing microcapsules: observation of coexistence of ordered and rotator phases.

In the present investigation, the crystallization and phase transition behaviours of normal alkane (n-docosane) in microcapsules with a mean diameter of 3.6 µm were studied by the combination of differential scanning calorimetry (DSC), temperature-dependent X-ray diffraction (XRD) and variable-temperature solid-state nuclear magnetic resonance (VT solid-state (13)C NMR). The DSC and VT solid-state (13)C NMR results reveal that a surface freezing monolayer is formed prior to the bulk crystallization of the microencapsulated n-docosane. More interestingly, it is confirmed that after the bulk crystallization, the ordered triclinic phase coexists with the rotator phase I (RI) for the microencapsulated n-docosane. We argue that the reduction of the free energy difference between the two phases, resulting from the microencapsulation process, leads to the coexistence of the ordered triclinic and rotator phases of the normal alkanes.

Solid-solid phase transition of n-alkanes in multiple nanoscale confinement.

The crystallization behavior of n-C(19)H(40)/SiO(2) nanosphere composites was investigated by a combination of differential scanning calorimetry (DSC) and temperature-dependent X-ray diffraction (XRD). Three kinds of confined alkanes with different solid-solid phase transition supercoolings and a surface (or interface) freezing monolayer of n-C(19)H(40) at the bulk liquid/SiO(2) interface were found in the composites at high SiO(2) loading. The surface freezing monolayer induces the chain packing of bulk alkanes by forming a 2D close-packed arrangement without long-range positional ordering in 3D space. A homogeneous nucleation and growth mechanism is found for the solid-solid transition in confined geometry, in which the supercooling of the transition is sensitive to the confined size.