STUDY ON THE THROUGH-SPACE AND THROUGH-BOND INTERACTIONS IN TRICYCLO 4,2,2,2 DODECADIENE-1.5

Through-space interactions of pi orbiatl and sigma orbital in molecule tricycle 4,2,2,2,dodecadiene -1.5 were studied by means of DV-X alpha SVF method using a model molecule that consists of two ethylenes with interdeck distance D. The results show the through-space interactions of the title molecule decrease with the increasing of D,the through-space interactions of pi orbital are larger than that of sigma orbital. Furthermore, through-bond interactions of the pi orbtial and sigma orbital were analyzed basing on the calculations of the electronic structure of the title molecule. Both through-space and through-bond interactions are Large and,the net interactions are small. The calculated ionization potential energies of the title molecule which were obtained by transition-state procedure are in good agreement with the PE spectroscopy.

Construction of chiral through-space luminophores via symmetry breaking triggered by sequenced chlorination

The construction of molecular chirality is crucial for exploring novel luminophores with chiroptical properties.Classic asymmetric synthesis of chiral center or axial is not powerful enough on through-space architecture.Accessible methodologies for breaking molecular symmetry could be promising but remain less investigated.Herein,we report a novel methodology for constructing chiral through-space luminophores via simple chlorination on bridged carbazole motifs.The chlorination breaks the molecular symmetry and thus results in molecular chirality by eliminating the mirror plane or rotating axis.Interestingly,continuous multiple chlorinations can rebuild and break the symmetry of the skeleton in succession.Several chiral and achiral isomeric analogues are synthesized and characterized with impressive chiroptical properties.Results of chiral high performance liquid chromatography(HPLC),single-crystal X-ray diffraction,kinetic racemization,and chiroptical property investigation demonstrate the effectiveness of our rational design strategy.It provides a feasible methodology for exploring novel chiral luminescent materials based on versatile though-space skeletons.

Acceptor modulation for improving thermally activated delayed fluorescence emitter in through-space charge transfer on spiroskeletons

Through-space charge transfer(TSCT)is regarded as an effective way to develop thermally activated delayed fluorescence(TADF)emitters.Based on this strategy,many molecular frameworks have been proposed,among which spirobased scaffolds have been extensively studied due to their unique advantages.In this work,we developed three emitters SPS,SPO,and SPON,which were constructed with the same donor and various acceptors to explore the influence of acceptor modulation at the C9 position of fluorene for spirostructure TSCT emitters.The results show that the acceptor with too weak electronwithdrawing ability will cause the emitter to not have TADF properties,while the acceptor with too much steric hindrance will weaken the face-to-faceπ-πstacking interaction between donor/acceptor(D/A).Since SPO balances the electron-withdrawing strength and steric hindrance of the acceptor,it achieves the highest external quantum efficiency(EQE)of 17.75%.This work shows that appropriate acceptor selection is essential for the TADF properties and high efficiency of the spirobased scaffold TSCT emitter.

Controllable Secondary Through-Space Interaction and Clusteroluminescence

Nonconjugated clusteroluminogens(CLgens),such as proteins and polystyrene,have become increasingly important in photophysics.They show many advantages over traditional conjugated dyes with fused aromatic rings in biological applications.However,CLgens have historically been unheeded because of their weak visible emissions in the aggregate state,namely clusteroluminescence(CL).Changing the electronic structures of CLgens by precisely regulating the intramolecular throughspace interaction(TSI)to improve their photophysical properties remains an enormous challenge.Herein,we propose a general strategy to construct a higher-level intramolecular TSI,namely secondary TSI constructed by the primary TSI and a TSI linker,in multi-aryl-substituted alkanes(MAAs).By introducing methyl and phenyl into 1,1,3,3-tetraphenylpropane,the modified MAAs show efficient CL with high luminescence quantum yield(-40%)and long emission wavelength(-530 nm).Then,comprehensive experiments and theoretical studies demonstrate that molecular rigidity and overlap of subunits play pivotal roles in improving these hierarchical TSIs.This work not only provides a feasible strategy to achieve controllable manipulation of hierarchical TSIs and CL but also establishes comprehensive TSI-based aggregate photophysics.

Synthesis and Properties of a Through-Space Interacting Diradicaloid

Knowledge about electronic structures is important to gain an understanding of the unique functional properties of diradicaloids.In this study,we synthesized and characterized a diradicaloid in which two phenalenyl radical sites are coupled antiferromagnetically via a through-space interaction.The results of quantum chemical,physicochemical(^(1)H NMR,electronic absorption,cyclic voltammetry,SQUID,ESR),and chemical reactivity studies show that this diradicaloid has singlet diradical character.An assessment of the nature of the bonding interaction between two radical sites in this species using DFT calculations demonstrates that a small spatial overlap between the two SOMOs in this diradicaloid provides an efficient electron exchange path for the singlet state to be substantially lower in energy than the triplet state.

Through-space charge transfer blue polymers containing acridan donor and oxygen-bridged triphenylboron acceptor for highly efficient solution-processed organic light-emitting diodes

Three kinds of through-space charge transfer(TSCT)blue polymers containing non-conjugated polystyrene backbone together with spatially-separated acridan donor and oxygen-bridged triphenylboron acceptors having different substituents of tert-butyl,hydrogen and fluorine are designed and synthesized.The designed TSCT blue polymers possess photoluminescence quantum yields up to 70%in solid-state film,single-triplet energy splitting below 0.1 eV,and typical thermally activated delayed fluorescence(TADF)effect.Meanwhile,the resulting polymers exhibit aggregation-induced emission(AIE)effect with emission intensity increased by up to^27 folds from solution to aggregation state.By changing the substituent of acceptors to tune the charge transfer strength,blue emission with peaks from 444 to 480 nm can be realized for the resulting polymers.Solution-processed organic light-emitting diodes based on the polymers exhibit excellent device performance with Commission Internationale de L’Eclairage(CIE)coordinates of(0.16,0.27),together with the maximum luminous efficiency of 30.7 cd A-1 and maximum external quantum efficiency of 15.0%,which is the best device efficiency for blue TADF polymers.

Through-Space Conjugation: A Thriving Alternative for Optoelectronic Materials

Efficient electronic coupling is the key to constructing optoelectronic functionalπsystems.Generally,the delocalization ofπelectrons must comply with the framework constructed by covalent bonds(typicallyσbonds),representing classic through-bond conjuga-tion.However,through-space conjugation offers an alternative that achieves spatial electron communica-tionwith closely stacked π systems instead of covalent bonds thus enabling multidimensional energy and charge transport.

Through-space charge transfer polymers for solution-processed organic light-emitting diodes

Through-space charge transfer(TSCT)polymers are an attractive class of luminescent polymers with spatial donor/acceptor architecture and thermally activated delayed fluorescence effect,different from conventional luminescent polymers with conjugated donor-acceptor structure and through-bond charge transfer emission.Their emission comes from the intramolecular charge transfer by through-space pathway because the donor and acceptor segments are spatially proximate to each other in each repeating unit but are physically separated by nonconjugated polymer backbone.In this review,recent advances in TSCT polymers with linear,bottlebrush,and dendritic architectures are presented,with the focus on their molecular design,photophysical behavior,and device performance.We hope that this review shall provide a useful insight of new luminescent polymers with TSCT effect for use in solution-processed organic light-emitting diodes.

Recent advances of folded tetraphenylethene derivatives featuring through-space conjugation

Through-space conjugated molecules are interesting building blocks for the construction of functional materials that allow multi-dimensional transport of carrier and energy.However,the well explored through-space conjugated molecules are quite limited,which defers their structure-property correlation establishment and wide-scale application.In this review,we introduce a kind of newly-emerging folded tetraphenylethene derivatives featuring through-space conjugation.Their synthesis,crystal and electronic structures,and optical properties are described,and their representative applications as bipolar charge-transporting materials in organic light-emitting diodes and as single-molecule wires in molecular devices are presented,which are anticipated to provide guidance for the further expansion of through-space conjugated systems.

Carbazole ring: A delicate rack for constructing thermally activated delayed fluorescent compounds with through-space charge transfer

Three carbazole derivatives, Ac PTC, Px PTC and Pt PTC, consisting of two 9,9-dimethyl-9,10-dihydroacridine,phenoxazine or phenothiazine donor groups and one diphenyltriazine acceptor group fixed at 1,8,9-positions of a single carbazole ring via phenylene, are designed and synthesized. X-ray diffraction analysis of Ac PTC reveals that there exist multiple π-π interactions between the donor and acceptor groups to form a sandwich-like structural unit with edge-to-face interaction model. The compounds thus show obvious thermally activated delayed fluorescence with through-space charge transfer character and possess considerable photoluminescence quantum yields of up to 73% in doped films with sky-blue to yellow emissions. The solution-processed electroluminescent devices achieve the highest maximum external quantum efficiencies of 10.0%, 11% and 5.6% for Ac PTC, Px PTC and Pt PTC, respectively, with small efficiency roll-offs.

Ⅰ期非小细胞肺癌患者肺穿刺活检是否增加胸膜复发和气腔播散的风险

近年来,随着肺结节的比例升高,术前经皮肺穿刺活检或经支气管镜活检越来越受到重视。大量临床证据也证实,Ⅰ期非小细胞肺癌(non-small cell lung cancer,NSCLC)的肺穿刺活检是安全可行的。但是,由于肺磨玻璃结节的组织学特点,与实性结节相比穿刺时更容易发生出血或咳嗽,肿瘤细胞在血流或气流冲击下可能会沿着肺泡壁或针道种植,导致胸膜复发和气腔播散(spread through air spaces,STAS),尤其是胸膜下结节合并有脏层胸膜侵犯和淋巴细胞浸润时需要慎重选择。

肺癌气道播散的影像学研究进展

肺癌气道播散(STAS)是指肿瘤细胞以微乳头状细胞团、实性细胞巢或单个细胞等形式存在于主瘤体之外的气道中。随着肺癌研究的不断深入,预测肺癌STAS在诊治和预后中有重要的价值,因此在2015年世界卫生组织将其确定为肺腺癌的一种新的侵袭方式。近年来,利用影像学方法预测STAS的有无已经成为研究的热点。目前相关研究的结果已证实了影像学预测STAS的可行性,进一步深入的研究对发现更加可靠和准确的影像学预测方法十分必要。本文就STAS的病理学、临床意义及影像学方面的研究进展予以综述。

肺腺癌病理分级与肿瘤气道播散及脉管侵犯的相关性

目的:探究新版肺腺癌分级系统与气道播散及脉管侵犯的相关性。方法:回顾性分析四川省肿瘤医院2021年行肺癌手术且经术后病理确认浸润性肺腺癌的患者,采集患者临床及病理信息,根据IASLC发布的新浸润性肺腺癌分级标准将患者分为3组,低分化组(III级)、中分化组(II级)、高分化组(I级)。分析患者术后临床病理特征及基因型与分级的关系。结果:单因素分析显示,低分化肿瘤与老龄、男性、实性结节、肺叶切除术和侵袭性特征(肿瘤大小、淋巴结转移、分期、气道播散、脉管浸润、胸膜浸润)相关。且与中高分化肿瘤具有显著性差异(P<0.05)。多因素分析显示肿瘤影像学特征、气道播散、脉管侵犯是独立因素。对行基因检测人群分析,EGFR突变在三组间无统计学意义(P>0.05)。余基因型无法评估与分级相关性。结论:低分化肿瘤与气道播散及脉管侵犯相关。

气道播散与肺腺癌临床病理危险因素相关性分析

目的探讨气道播散(STAS)在肺腺癌中的意义及与临床病理危险因素的相关性。方法选取2015-10—2022-10在涿州市医院和河北一洲肿瘤医院接受手术切除术的228例肺腺癌患者为研究对象。通过苏木精-伊红染色判断STAS情况;分析STAS与临床病理危险因素的相关性。结果STAS与性别、吸烟、组织学类型、T分期、淋巴结转移、脉管神经侵犯和肺膜侵犯相关(P<0.05);与年龄无关。生存分析发现,伴STAS的总生存时间低于无STAS的患者(P<0.05)。结论STAS在肺腺癌预后中具有重要的价值,STAS和临床病理危险因素相结合可以提高肺腺癌预后评估的准确性和可靠性,建议在常规病理报告中纳入此项指标,为肺腺癌患者的治疗和预后评估提供更为科学、全面的依据。

不同内固定术治疗创伤性胸腰椎骨折的效果对比

目的:比较不同内固定术治疗创伤性胸腰椎骨折的效果。方法:选取2021年1月-2022年1月仁怀市中医院收治的胸腰椎骨折患者100例作为研究对象,采用随机数字表法分为对照组和观察组,各50例。对照组采用经皮入路椎弓根钉棒系统内固定治疗,观察组采用经椎旁肌间隙入路椎弓根钉棒系统内固定治疗。比较两组围术期指标及骨折愈合时间、骨代谢活性指标、围术期并发症、疼痛程度与功能障碍情况。结果:两组手术时间、术中出血量比较,差异无统计学意义(P>0.05);观察组住院时间、骨折愈合时间短于对照组,差异有统计学意义(P<0.001)。术后1个月,两组骨钙素(BGP)、骨保护素(OPG)水平高于术前,Ⅰ型胶原C端肽(CTX-Ⅰ)水平低于术前,差异有统计学意义(P<0.05);术后1个月,观察组BGP和OPG水平高于对照组,CTX-Ⅰ水平低于对照组,差异有统计学意义(P<0.05)。观察组并发症发生率低于对照组,差异有统计学意义(P=0.029)。术后3个月,两组视觉模拟评分、Oswestry功能障碍指数均降低,观察组低于对照组,差异有统计学意义(P<0.001)。结论:两种手术方式均具有良好的预后效果,但经椎旁肌间隙入路的椎弓根钉棒系统内固定方法效果更加显著,在提高患者围术期指标与提高骨代谢活性指标的同时,还可减少并发症,减轻疼痛程度,值得推广。

经椎旁肌间隙入路结合伤椎置钉内固定系统对胸腰椎骨折的治疗效果及对患者椎体前缘高度和伤椎楔变指数的影响

目的探讨经椎旁肌间隙入路结合伤椎置钉内固定系统对胸腰椎骨折的治疗效果及对患者椎体前缘高度和伤椎楔变指数的影响。方法选取2019年1月至2022年1月海东市平安区中医院收治的56例胸腰椎骨折患者作为研究对象,根据手术方式分为A组与B组,每组28例。A组采用经椎旁肌间隙入路结合伤椎双侧置钉内固定治疗,B组采用经椎旁肌间隙入路跨伤椎常规置钉治疗,比较两组基本手术指标、脊柱功能恢复情况、并发症发生情况、生命质量。结果A组下床活动及骨折愈合时间短于B组(P<0.05);两组术中出血量比较差异无统计学意义;术后3个月,两组椎体前缘高度、IVW均高于术前,Cobb角、ODI评分均低于术前,且A组椎体前缘高度、IVW高于B组,Cobb角、ODI评分均低于B组,差异有统计学意义(P<0.05)。A组并发症发生率低于B组,差异有统计学意义(P<0.05)。术后3个月,两组生理机能、生理职能、情感职能、精神健康、生命活力、社会功能、躯体疼痛、总体健康评分均高于术前,且A组均高于B组,差异有统计学意义(P<0.05)。结论经椎旁肌间隙入路结合伤椎双侧置钉内固定治疗胸腰椎骨折患者疗效显著,可有效改善患者脊柱功能,提高患者生命质量,减少并发症,值得临床推广应用。

地铁域地下空间综合可达性测度及优化路径研究——以青岛市为例

为实现地铁域地下空间在功能利用和空间可达性维度的规划优化,以青岛市地铁域地下空间为研究区域,依托POI、OSM等开放多源数据构建可达性评价指标体系,并结合空间句法模型、CRITIC算法对地铁域地下空间的综合可达性进行量化测度。基于节点-场所模型与可达性测度结果,有效识别了青岛市地铁域地下空间的失衡利用单元,并根据地下空间开发强度、地面建筑开发强度、区位交通条件3个层面的单元类别分类制定了相应的规划优化原则及优化策略。

肺癌经气腔播散的临床特征与外科治疗

目的 对肺癌经气腔播散(STAS)的临床、病理及影像特征进行分析,并探讨其对外科治疗决策的影响。方法 选取2021年1月至12月郑州大学第一附属医院收治的Ⅰ~Ⅲ期肺癌手术患者作为研究对象,收集其临床、病理及影像学检查信息并分析。结果 STAS的存在与肺癌的组织学类型(P=0.009)、组织学分化(χ^(2)=33.935,P<0.001)、有无脉管侵犯(χ^(2)=8.728,P=0.004)、计算机断层扫描(CT)图像中实性成分占比(Z=2.697,P=0.007)、结节形状(χ^(2)=6.646,P=0.035)、有无中央低密度区(χ^(2)=11.227,P=0.001)有关,且STAS阳性患者与较高的浸润性腺癌占比、较低的组织学分化、较高的脉管侵犯率、CT图像中较高的实性成分占比、结节形状不规则或为类圆形及结节含有中央低密度区等关联。在77例≤2 cm结节中,STAS的存在则与较大的实性部分直径、较高的实性成分占比及结节含有中央低密度区密切关联。结论 STAS阴性和阳性患者的病理及影像学特征存在差异,分析这些差异有助于指导外科手术决策。

策展视角下城市家具促进社区空间微更新研究

为了贯彻“十四五”规划中完善大中城市宜居宜业功能的目标,本研究旨在基于策展的视角下利用城市家具解决老旧社区的空间微更新问题。研究试图探讨策展、城市家具与城市微更新之间的逻辑关联,剖析策展视角下城市家具在空间微更新中的设计原则,再取2021上海城市空间艺术季四平展区作为具体实践项目,以策展作为设计手段,统筹城市家具作为人与空间之间的媒介,从而达到激活老旧社区空间的目的,最后总结出“以展促建”模式的优势及其对城市微更新的研究意义。通过理论与实践双重角度推动社区空间微更新,促进了城市可持续发展,迎合了“十四五”规划的国家战略意图。

基于数据校验时空图的卫星网络连接计划设计

针对低轨卫星网络中网络时空连通性和流量阻塞的问题,综合考虑了星间链路状态、卫星能效和负载状态,提出了一种基于数据校验时空图的连接计划设计(data check time-space graph-contact plan design, DCTSG-CPD)方案。首先,构建基于电池模型的数据校验时空图(data check time-space graph, DCTSG),并以星间链路和卫星能源为约束,将连接计划设计建模为最大化吞吐量问题;其次,在DCTSG的基础上,通过对校验数据和转发数据的对比判断网络拥塞状态,根据卫星节点负载和星间链路流量阻塞状态,生成可用连接计划(contact plan, CP);最后,设计适应度函数以评价可用CP的优劣,提出基于数据校验的遗传算法更新CP以生成吞吐量最大化的最佳CP。仿真结果表明,所提DCTSG-CPD方案不仅能够提升吞吐量,而且可以有效降低数据交付时延。