Abstract This work systematically investigates the bulk self-assembly behavior of binary and ternary blends of discrete giant polymer chains, focusing on the impact of chain-length asymmetry (γ), number fraction of long chains (nA), and regio-configuration. In binary blends with large chain-length disparity at low nA (0.1–0.17), a nanoscale phase coexistence with fixed domain spacings emerges, manifesting as two distinct lamellar phases with invariant periodicities. This behavior directly reflects size incompatibility rather than continuous mixing. Separately, a microconfinement-driven ordering effect is demonstrated: intrinsically disordered long chains (e.g., p-C8D) are forced into ordered lamellar structures when blended with a minor fraction of ordered short chains, a process confirmed to be thermally reversible. Regio-configuration further modulates the swollen lamellar spacing by altering chain conformation. Extending to ternary blends, a third component with intermediate chain length promotes ordered hexagonal (HEX) or body-centered cubic (BCC) phases from initially disordered binary systems, we attribute this to a “chain-length complementation” effect, where the third component relieves packing frustration caused by chain-length disparity. These findings reveal how chain-length distribution shape, regio-regularity, and multicomponent synergy regulate nanostructures, offering a rational route toward ordered nanomaterials with tunable lattice symmetries.
In this study, we modularly prepared a library of giant molecules using molecular nanoparticles - polyhedral oligomeric silsesquioxane (POSS) - as repeat units, with precise control over composition, regio-configuration, and sequence. Benefiting from the enlarged unit size, the assembly behaviors of these giant molecules are found to be sensitive to subtle structural variations. The precise chemical structure rules out molecular "defects" and serves as an ideal platform to resolve minute differences. The regio-configuration directly impacts the spatial arrangement of the neighboring POSS units, resulting in distinct phase behaviors. Molecular geometry, which stems from the monomer sequence, plays a crucial role in the self-assembly process. Simply changing the position of the alkyl ligands on the peripheries of particles generates substantial differences in the period spacing and phase stability, and in some cases even triggers a phase transition toward distinct structures.
In this study, a series of polyhedral oligomeric silsesquioxane (POSS)-based three-component triblock giant molecules were designed and prepared to highlight the critical influence of regio-configuration and molecular geometry on the self-assembly behaviors. On the one hand, regio-configuration exerts additional constraints on molecular packing, resulting in ordered structures with different lattice sizes and phase stability. On the other hand, molecular geometry originating from sequence variations significantly affects their spatial arrangements. Both factors together determine the assembled structures. The nanosized building blocks amplify the pivotal role of seemingly subtle molecular differences, providing an ideal platform to understand the underlying details that have been largely overlooked in polymer coils.
Rational design of “giant” building blocks promotes the modular construction of polymeric counterparts at a large length scale. In this study, a series of biscylooctyne- and bisazide-functionalized polyhedral oligomeric silsesquioxane (POSS) monomers with different regio-configurations were synthesized. Homo and alternating giant polymeric chains were then efficiently prepared by strain-promoted azide-alkyne cycloaddition (SPAAC) polymerization. The obtained monomers and polymers were characterized by proton nuclear magnetic resonance ( 1 H NMR), size exclusion chromatography (SEC), and matrix-assisted laser desorption ionization time-of-flight (MALDI-ToF) mass spectrometry. The influence of the feeding ratio, monomer concentration, and regio-configuration on the step-growth polymerization was investigated. Due to the large monomer size, the giant chains can be purified and fractionated by preparative SEC. This work provides a facile and efficient approach for the modular construction of main-chain polymers with nanosized building blocks.
目的 通过对1例新西兰籍华人ABO血型检测结果投诉的案例分析,探讨ABO血型检测结果的影响因素及入出境人员ABO血型检测方法的标准化.方法 接到投诉后,实验室对留样进行正反定型再测,并重新采血后送某三甲医院进行正定型玻片法和正反定型微柱凝胶法检测.结果 通过复测确定此例ABO血型检测结果为A型,此次投诉为无效投诉.结论 对有异议的ABO血型检测结果应同时采用另一种检测方法复检,并充分考虑检测试剂、被检人种族、疾病史等影响因素,规范入出境人员ABO血型检测复检流程,达到入出境人员ABO血型检测的标准化.
目的 通过对2018-2022年AFP、CEA、EB病毒抗体检测结果分析,了解健康体检人群检测阳性率.方法 采用ELISA方法对1 929例健康体检人群AFP、CEA、EB病毒抗体进行检测.结果 AFP阳性率为0.62%,CEA阳性率为0.21%,EBV-VCA-IgA抗体阳性率为2.38%.EBV-VCA-IgA检测的阳性率男性明显高于女性.结论 AFP、CEA、EB病毒抗体ELISA检测为有效的肿瘤检测初筛手段,需要结合临床进一步做出诊断.
目的 通过分析实验室不符合项的总体情况,探索不符合项分析在质量管理体系持续改进中的应用.方法 汇总分析2021-2022年不符合项的来源、分类、原因分析及整改措施.结果 不符合项共计48个,对应14个条款,其中7.7确保结果有效性20.83%,6.2人员、7.2方法的选择、验证和确认、8.3管理体系文件的控制均为12.50%.结论 提升质量管理的执行力、强化质量管理体系掌握程度和促进能力提升是目前质量管理体系持续改进的重点,加强不符合项分析对实验室质量工作的应用,促进实验室质量管理体系的运行效率.
目的 了解中山地区出国留学生的跨文化适应性现状及其影响因素,为提高留学生跨文化适应水平提供科学依据.方法 利用自行设计的跨文化适应调查问卷开展无记名测试,并对部分人员进行深度访谈.结论 中山地区出国留学生整体跨文化适应水平较好,出国前加强知识储备、建立良好的社会网络、文化自信以及出国前培训等都可以有效提高跨文化适应能力.
In this study, polyhedral oligomeric silsesquioxane (POSS) based giant triblock molecules with precisely defined regio-configuration are modularly prepared through highly efficient coupling reactions. The length of the linker connecting neighboring nanoparticles is elaborately designed to regulate the geometric constraints. The triblock molecules adopt a folded packing during phase separation, and the regio-configuration imparts direct influence on the self-assembly behaviors. The ortho-isomers form periodic structures with a larger domain size, larger interfacial curvature, and enhanced phase stability. The regio-effect is closely related to the length and symmetry of the linker. As the linker extends, the neighboring particles gradually decouple, and the regio-effect diminishes. The symmetry of the linker shows an even more profound impact. This work quantitatively scrutinized the role of the linker, opening an avenue for engineering the assembled structures with molecular precision.
Background Diabetic kidney disease (DKD) is a significant complication of diabetes and has garnered considerable attention. Our previous retrospective study indicated that Shenzhuo formula (SZF) potentially reduces macroalbuminuria secondary to DKD. Methods This trial is a 24-week, randomized, multicentric, double-blinded, double-dummy clinical trial. A total of 120 patients with DKD will be equally and randomly divided into two groups: SZF+ irbesartan simulator or irbesartan + SZF simulator. The 24-h urinary protein change from baseline to week 24 is the primary outcome measure. The secondary outcome measures include serum creatinine, estimated glomerular filtration rate, urinary albumin excretion rate, improvement in traditional Chinese medicine symptoms, fasting blood glucose, 2-h postprandial plasma glucose, hemoglobin A1c, cholesterol, triglycerides, high density lipoprotein, low density lipoprotein, blood pressure, albumin to creatinine ratio, and the Audit of Diabetes-Dependent Quality of Life 19. Our recruitment began in May 2015; currently, we have recruited 100 participants, with a designed maximum sample size of 120. The interim results were reviewed at N = 60, and continuing recruitment was recommended. This statistical analysis plan includes our approach to missing data imputation, primary and secondary outcomes analyses, and safety endpoints. Discussion This statistical analysis plan will standardize the clinical trial’s statistical analysis and avoid outcome selective reporting bias and data-driven analysis. This trial will provide further clinical evidence regarding the effectiveness of SZF in managing macroalbuminuria secondary to DKD. Trial registration Chinese Clinical Trial Registry ChiCTR-ICR-15006311. Registered on 26 May 2013. http://www.chictr.org.cn/showproj.aspx?proj=10862
The vastly expanding chemical and architectural parameter space of multiblock copolymers brings both opportunities and challenges for tailoring the structure and properties of a synthetic polymer. In this study, we reported a precise and concise multiblock model system to amplify the subtle structural variations and resolve the underlying phase principles. A series of giant polymeric chains based on polyhedral oligomeric silsesquioxane nanoparticles with an exact block number, regio-configuration, and sequence were designed and prepared. A close scrutiny of these sequence-/regio-isomers revealed that the interplay of geometric constraints, regio-configurations, and collective interactions dictates the self-assembled structures. Zigzag-packed lamellae with the layer normal perpendicular to the backbone were observed for the alternating chains, while a head-to-head arrangement with the lamellar normal along the chain direction was recognized in the case of block chains. Due to the geometric constraint, the alternating chains were exceedingly sensitive to the regio-regularity, leading to dramatically different phase stabilities. This work reveals the critical contribution of the block sequence and regio-configuration to phase behaviors, providing deeper insights toward rational structural engineering of multiblock copolymers.
Polymeric chains made of "giant" monomers at a larger length scale provide intriguing insights into the fundamental principles of polymer science. In this study, we modularly prepared a library of discrete amphiphilic polymeric chains using molecular nanoparticles as repeat units, with exact control of composition, chain length, surface property, and regio-configuration. These giant polymeric chains self-assembled into a rich collection of highly ordered phases. The precise chemical structure and uniform chain length eliminate all the inherent molecular "defects", while the nanosized monomer amplifies minute structural differences, providing an ideal platform for a systematic scrutiny of the self-assembly behaviors at a larger length scale. The compositional and regio-configurational contribution was carefully studied. The regio-regularity is found to have a direct and profound impact on the chain conformation, leading to a distinct molecular packing scheme and therefore shifting the phase boundaries. With increasing the length of the linker, the regio-constraint gradually diminishes, and the neighboring particles would eventually be decoupled.
Hydrodynamic cavitation (HC) has been widely considered a promising technique for industrial-scale process intensifications. The effectiveness of HC is determined by the performance of hydrodynamic cavitation reactors (HCRs). The advanced rotational HCRs (ARHCRs) proposed recently have shown superior performance in various applications, while the research on the structural optimization is still absent. The present study, for the first time, identifies optimal structures of the cavitation generation units of a representative ARHCR by combining genetic algorithm (GA) and computational fluid dynamics, with the objectives of maximizing the total vapor volume, Vvapor , and minimizing the total torque of the rotor wall, M→z . Four important geometrical factors, namely, diameter (D), interaction distance (s), height (h), and inclination angle (θ), were specified as the design variables. Two high-performance fitness functions for Vvapor and M→z were established from a central composite design with 25 cases. After performing 10,001 simulations of GA, a Pareto front with 1630 non-dominated points was obtained. The results reveal that the values of s and θ of the Pareto front concentrated on their lower (i.e., 1.5 mm) and upper limits (i.e., 18.75°), respectively, while the values of D and h were scattered in their variation regions. In comparison to the original model, a representative global optimal point increased the Vvapor by 156% and decreased the M→z by 14%. The corresponding improved mechanism was revealed by analyzing the flow field. The findings of this work can strongly support the fundamental understanding, design, and application of ARHCRs for process intensifications.
Water (as hydrogen) plays an important role in geodynamics of our planet, not only because it enhances the diffusion and creep, but also because it lowers the melting temperature of the rock/mantle (i. e. , 'flux melting'). Furthermore, fluids significantly affect the geophysical properties of rock mass or the evolution of geological structures, even trigger geological disasters. Water-induced influence runs through the whole dynamic process of the plate subduction. However, the deep slab dehydration (at depth >300 km) is controversial, and the dynamic process of water migration in the subduction zone and its geophysical implications are still poorly understood. Two-dimensional chemical-thermal-mechanical coupling models, which used northeastern China as example, were implemented to simulate the slab subduction process, with particular attention paid to the whole continuous dynamics process of the fluid/water migration. The simulation and analysis results show that the process of water migration during plate subduction can be divided into three stages : ocean crust hydration, shallow (middle) slab dehydration, and deep slab dehydration. Furthermore, the mechanism of water seepage channel formation, water seepage and hydration reaction of plate and mantle material was revealed in the hydration process of ocean crust; the effects of shallow (middle) slab dehydration process on the formation of island arc, back-arc basin, low-velocity zone and the similar to 410 km discontinuity were explained; the phenomenon of deep slab dehydration was observed in the numerical simulation, which can explain the causes of some inland volcanoes as well as mantle plumes (magma plumes) and deep-source earthquakes in some areas. This study demonstrates the geophysical implications of water migration during plate subduction.
随着海外中国留学生人数不断增加,异域文化的冲击使留学生面临的跨文化适应问题越来越受到关注.本文就国内外对海外中国留学生跨文化适应影响因素的研究成果进行综述,分析了跨文化适应的主要影响因素,结合国内留学生教育情况,借鉴目前国内外留学生心理健康教育方法,提出加强出国前培训、构建预警机制、建立多元化社会支持系统等方法,并依据国际旅行卫生保健中心工作实际情况提出了增强跨文化适应测评,建立跨文化适应档案和咨询室的建议.
Discrete oligo- and polyesters are highly attractive for a wide range of investigations because of their great fidelity on structure-property relationships. Even though numerous synthetic approaches have been developed, a more versatile synthetic platform with broad group tolerance is still desired. Herein, we report an iterative exponential growth strategy for efficient synthesis of discrete oligo- and polyesters, employing an optimized protective group pair, namely, TBDPS ether and t-butyl ester. The versatility of the strategy is demonstrated by facile preparation of several structurally diverse discrete oligo- and polyesters under mild, safe, and scalable reaction conditions, with the number of repeat units up to 256. Moreover, the contributions of the terminal protective groups on the melting and crystallization behaviors of discrete oligo- and poly(epsilon-caprolactone)s were investigated. With this robust synthetic platform, various functional moieties can be readily incorporated into polyester chains, and a myriad of applications of polyesters could thus be reasonably anticipated.
In this work, the synthesis and modulation as well as the mechanisms of a series of 3-aminomaleimide fluorophores based on the air oxidation of 3-aminosuccinimides are reported through combined experimental and computational studies. The central observations include the following: (1) the evident fluorescence observed in the Michael addition reaction of amine to maleimide was attributed to the formation of 3-aminomaleimide fluorophores via the air oxidation process, (2) the chemical conversion from aminosuccinimide to aminomaleimide is thermodynamically favourable and a series of primary and secondary amines are compatible with this reaction, and (3) the steric and electronic effects exerted by amino substituted groups can effectively inhibit twisted intramolecular charge transfer (TICT) and markedly improve the quantum yields of 3-aminomaleimide fluorophores. As a proof-of-concept, the 3-aminomaleimides manifested themselves as efficient fluorophores that can be readily applied in solid emission for optical waveguides and emissive oligomers for bioimaging. Our findings establish a new frontier on the innovative synthesis and accurate modulation of simple luminescent structures for versatile, high-performance functional materials.
Cocrystallization has been used extensively to optimize the physicochemical properties of active pharmaceutical ingredients (APIs), such as stability, dissolution, and bioavailability. This review summarizes the history and development of cocrystals, the differences between pharmaceutical cocrystals and salts, and the mechanism underlying the improvement of dissolution through cocrystallization. The correlation of in vitro dissolution and in vivo absorption data (IVIVC) of cocrystals has been discussed as well. Subsequently, guidelines for regulatory classification of cocrystals by the U.S. Food and Drug Administration (FDA) and European Medicines Agency (EMA) are introduced. Finally, d-α-tocopherol is used as an example to demonstrate the potential of cocrystals in patent generation.
近断层地震动具有幅值高、高频成分丰富等特点,对短周期结构威胁甚大.为模拟近断层地震动作用,以精河地震为例,利用基于地震烈度转换方法的地震动衰减关系和随机有限断层方法模拟主震在6个场点产生的地震动,分析不同方法估计的峰值加速度与加速度反应谱衰减特征;同时选取17个场点的地震动,分析断层上盘效应,从而更加合理地估计近断层地震动.结合精河Ms6.6地震的发震构造分析,确定库松木切克山前断裂的分支精河水文站断裂为该地震的发震断层.研究结果表明:①随机方法估计的PGA与+σ误差项衰减关系短轴估计的PGA接近,两者可能都比较接近实际PGA;相较于衰减关系法,基于有限断层模型的随机方法,优势在于能较好模拟近断层地震动特征;②近断层地震动受上盘效应影响显著,断层距相同的上下盘场点,上盘地震动明显大于下盘;③对于有历史地震及地震数据的地区,可以基于已有地震数据,使用多种方法联合估计地震动参数,为工程场地地震安评提供参考依据.
Lanqin Oral Liquid is a Chinese patent medicine which contains Isatidis Radix, Scutellariae Radix, Gardeniae Fructus, Phellodendri Chinensis Cordex and Sterculiae Lychophorae Semen. It is known for the pharmaceutical effect on the upper respiratory tract infection as it is beneficial for relieving the swelling of pharyngeal. In terms of Chinese medicine, it offers a clearing action on heat and toxic materials. According to the principle of Chinese medicine, different diseases can be treated by the same therapy as long as they have the same syndrome. Based on this unique diagnosis and treatment approach, Lanqin Oral Liquid was applicable to diseases with syndrome of excessive heat in lung and stomach. It was therefore commonly be used in the therapeutic approach towards hand, foot and mouth disease as well. However, no systematic evaluation had yet been done to verify this Chinese patent medicine on the efficacy and clinical safety for the disease. In order to achieve the manner of evidence-based medicine, this study had adopted a systematic review and Meta-analysis to evaluate the efficacy and safety of Lanqin Oral Liquid in the treatment of hand, foot and mouth disease. All related randomized controlled trials(RCT) were searched in the following data bases: CNKI, WanFang, VIP, SinoMed, Cochrane Library and PubMed. Based on the method provided by the Cochrane collaboration, the study assessed the quality of papers selected and RevMan 5.3 software was used to perform Meta-analysis. Totally 24 studies were included with 3 491 sample size, which 1 826 cases were treatment group and 1 665 cases were control group. From the results of Meta-analysis, the total effective rate of combination of Lanqin Oral Liquid and Western medicines shown better than Western medicine alone in the treatment for hand, foot and mouth di-sease, but mild adverse event were also found(RR=1.20,95%CI[1.16,1.23],P<0.000 01). Incidence of adverse reaction between experimental and control group was statistically insignificant(RR=1.16, 95%CI[0.79, 1.70], P=0.45). No conclusion was able to made in terms of the remission time of clinical symptoms, as the studies included were not qualified for Meta-analysis. As a matter of fact, the number of existing studies related to the Lanqin Oral Liquid were limited with poor quality as well. In other words, high quality studies were essential to further evaluate the efficacy and safety of Lanqin Oral Liquid.