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1.
Sci Rep ; 14(1): 10697, 2024 May 10.
Artículo en Inglés | MEDLINE | ID: mdl-38730236

RESUMEN

The object scale of a small object scene changes greatly, and the object is easily disturbed by a complex background. Generic object detectors do not perform well on small object detection tasks. In this paper, we focus on small object detection based on FocusDet. FocusDet refers to the small object detector proposed in this paper. It consists of three parts: backbone, feature fusion structure, and detection head. STCF-EANet was used as the backbone for feature extraction, the Bottom Focus-PAN for feature fusion, and the detection head for object localization and recognition.To maintain sufficient global context information and extract multi-scale features, the STCF-EANet network backbone is used as the feature extraction network.PAN is a feature fusion module used in general object detectors. It is used to perform feature fusion on the extracted feature maps to supplement feature information.In the feature fusion network, FocusDet uses Bottom Focus-PAN to capture a wider range of locations and lower-level feature information of small objects.SIOU-SoftNMS is the proposed algorithm for removing redundant prediction boxes in the post-processing stage. SIOU multi-dimension accurately locates the prediction box, and SoftNMS uses the Gaussian algorithm to remove redundant prediction boxes. FocusDet uses SIOU-SoftNMS to address the missed detection problem common in dense tiny objects.The VisDrone2021-DET and CCTSDB2021 object detection datasets are used as benchmarks, and tests are carried out on VisDrone2021-det-test-dev and CCTSDB-val datasets. Experimental results show that FocusDet improves mAP@.5% from 33.6% to 46.7% on the VisDrone dataset. mAP@.5% on the CCTSDB2021 dataset is improved from 81.6% to 87.8%. It is shown that the model has good performance for small object detection, and the research is innovative.

2.
Nat Commun ; 15(1): 3668, 2024 Apr 30.
Artículo en Inglés | MEDLINE | ID: mdl-38693122

RESUMEN

Mechanoluminescence, featuring light emission triggered by mechanical stimuli, holds immense promise for diverse applications. However, most organic Mechanoluminescence materials suffer from short-lived luminescence, limiting their practical applications. Herein, we report isostructural doping as a valuable strategy to address this challenge. By strategically modifying the host matrices with specific functional groups and simultaneously engineering guest molecules with structurally analogous features for isostructural doping, we have successfully achieved diverse multicolor and high-efficiency persistent mechanoluminescence materials with ultralong lifetimes. The underlying persistent mechanoluminescence mechanism and the universality of the isostructural doping strategy are also clearly elucidated and verified. Moreover, stress sensing devices are fabricated to show their promising prospects in high-resolution optical storage, pressure-sensitive displays, and stress monitoring. This work may facilitate the development of highly efficient organic persistent mechanoluminescence materials, expanding the horizons of next-generation smart luminescent technologies.

3.
IEEE Trans Cybern ; 54(4): 2618-2627, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-37819825

RESUMEN

This article mainly studies the problem of impulse consensus of multiagent systems under communication constraints and time delay. Considering the limited communication bandwidth of the agent, global and partial saturation constraints are considered. In addition, so as to further improve communication efficiency by reducing communication frequency, the novel control protocol combining event-triggered strategy and general impulse control protocol is proposed. Under this kind of novel control protocol, the communication frequency of multiagent systems can be reduced while avoiding "Zeno behavior." Through theoretical analysis, sufficient conditions for the systems to achieve consensus are obtained for the above two saturation constraint cases. In the end, the effectiveness of the novel protocols is proved by providing two different simulation instances.

4.
Angew Chem Int Ed Engl ; 62(45): e202310335, 2023 Nov 06.
Artículo en Inglés | MEDLINE | ID: mdl-37726259

RESUMEN

Dual-mode emission materials, combining phosphorescence and delayed fluorescence, offer promising opportunities for white-light afterglow. However, the delayed fluorescence lifetime is usually significantly shorter than that of phosphorescence, limiting the duration of white-light emission. In this study, a carbazole-based host-guest system that can be activated by both ultraviolet (UV) and visible light is reported to achieve balanced phosphorescence and delayed fluorescence, resulting in a long-lived white-light afterglow. Our study demonstrated the critical role of a charge transfer state in the afterglow mechanism, where the charge separation and recombination process directly determined the lifetime of afterglow. Simultaneously, an efficient reversed intersystem crossing process was obtained between the singlet and triplet charge transfer states, which facilitating the delayed fluorescence properties of host-guest system. As a result, delayed fluorescence lifetime was successfully prolonged to approach that of phosphorescence. This work presents a delayed fluorescence lifetime improvement strategy via doping method to realize durable white-light afterglow.

5.
Aging (Albany NY) ; 13(23): 25195-25212, 2021 12 13.
Artículo en Inglés | MEDLINE | ID: mdl-34898474

RESUMEN

Cholangiocarcinoma is a highly aggressive malignant tumor, and its incidence is increasing all over the world. More and more evidences show that the aberrant expression of circular RNAs play important roles in tumorigenesis and progression. Current studies on the expression and function of circRNAs in cholangiocarcinoma are scarce. In this study, circ-ZNF609 was discovered as a novel circRNA highly expressed in cholangiocarcinoma for the first time. The circ-ZNF609 expression is connected with the advanced TNM stage, lymphatic invasion and survival time in cholangiocarcinoma patients, and can be used as an independent prognostic factor for the patients. Circ-ZNF609 can promote the cholangiocarcinoma cells proliferation, migration and invasion in vitro, it can also catalyze the xenograft growth in vivo. The promoting effect of circ-ZNF609 on cholangiocarcinoma is achieved via oncogene LRRC1 up-regulation through targeting miR-432-5p by endogenous competitive RNA mechanism. In addition, transcription factor YY1 can bind to the promoter of ZNF609 to further facilitate the transcription of circ-ZNF609. RNA binding protein eIF4A3 can bind to the pre-mRNA of circ-ZNF609 which promotes the circ-ZNF609 circular formation. Overall, YY1/eIF4A3/circ-ZNF609/miR-432-5p/LRRC1 have a significant role in progression of cholangiocarcinoma, and circ-ZNF609 is expected to become a novel biomarker for targeted therapy and prognosis evaluation of cholangiocarcinoma.


Asunto(s)
Neoplasias de los Conductos Biliares/metabolismo , Proteínas de Ciclo Celular/metabolismo , Colangiocarcinoma/metabolismo , ARN Helicasas DEAD-box/metabolismo , Factor 4A Eucariótico de Iniciación/metabolismo , MicroARNs/metabolismo , ARN Circular/metabolismo , Factor de Transcripción YY1/metabolismo , Línea Celular Tumoral , Movimiento Celular , Proliferación Celular , Femenino , Humanos , Masculino , Persona de Mediana Edad , Invasividad Neoplásica
6.
Nature ; 599(7883): 67-73, 2021 11.
Artículo en Inglés | MEDLINE | ID: mdl-34732866

RESUMEN

Chemical doping is a key process for investigating charge transport in organic semiconductors and improving certain (opto)electronic devices1-9. N(electron)-doping is fundamentally more challenging than p(hole)-doping and typically achieves a very low doping efficiency (η) of less than 10%1,10. An efficient molecular n-dopant should simultaneously exhibit a high reducing power and air stability for broad applicability1,5,6,9,11, which is very challenging. Here we show a general concept of catalysed n-doping of organic semiconductors using air-stable precursor-type molecular dopants. Incorporation of a transition metal (for example, Pt, Au, Pd) as vapour-deposited nanoparticles or solution-processable organometallic complexes (for example, Pd2(dba)3) catalyses the reaction, as assessed by experimental and theoretical evidence, enabling greatly increased η in a much shorter doping time and high electrical conductivities (above 100 S cm-1; ref. 12). This methodology has technological implications for realizing improved semiconductor devices and offers a broad exploration space of ternary systems comprising catalysts, molecular dopants and semiconductors, thus opening new opportunities in n-doping research and applications12, 13.

7.
Nonlinear Dyn ; 104(4): 4671-4680, 2021.
Artículo en Inglés | MEDLINE | ID: mdl-33935366

RESUMEN

This work concentrates on the dynamic analysis including bifurcation and chaos of a discrete ecological developmental systems. Specifically, it is a prey-predator-scavenger (PPS) system, which is derived by Euler discretization method. By choosing the step size h as a bifurcation parameter, we determine the set consists of all system's parameters, in which the system can undergo flip bifurcation (FB) and Neimark-Sacker bifurcation (NSB). The theoretical results are verified by some numerical simulations. It is shown that the discrete systems exhibit more interesting behaviors, including the chaotic sets, quasi-periodic orbits, and the cascade of period-doubling bifurcation in orbits of periods 2, 4, 8, 16. Finally, corresponding to the two bifurcation behaviors discussed, the maximum Lyapunov exponent is numerically calculated, which further verifies the rich dynamic characteristics of the discrete system.

8.
J Am Chem Soc ; 143(3): 1539-1552, 2021 Jan 27.
Artículo en Inglés | MEDLINE | ID: mdl-33445867

RESUMEN

n-Type polymers with deep-positioned lowest unoccupied molecular orbital (LUMO) energy levels are essential for enabling n-type organic thin-film transistors (OTFTs) with high stability and n-type organic thermoelectrics (OTEs) with high doping efficiency and promising thermoelectric performance. Bithiophene imide (BTI) and its derivatives have been demonstrated as promising acceptor units for constructing high-performance n-type polymers. However, the electron-rich thiophene moiety in BTI leads to elevated LUMOs for the resultant polymers and hence limits their n-type performance and intrinsic stability. Herein, we addressed this issue by introducing strong electron-withdrawing cyano functionality on BTI and its derivatives. We have successfully overcome the synthetic challenges and developed a series of novel acceptor building blocks, CNI, CNTI, and CNDTI, which show substantially higher electron deficiencies than does BTI. On the basis of these novel building blocks, acceptor-acceptor type homopolymers and copolymers were successfully synthesized and featured greatly suppressed LUMOs (-3.64 to -4.11 eV) versus that (-3.48 eV) of the control polymer PBTI. Their deep-positioned LUMOs resulted in improved stability in OTFTs and more efficient n-doping in OTEs for the corresponding polymers with a highest electrical conductivity of 23.3 S cm-1 and a power factor of ∼10 µW m-1 K-2. The conductivity and power factor are among the highest values reported for solution-processed molecularly n-doped polymers. The new CNI, CNTI, and CNDTI offer a remarkable platform for constructing n-type polymers, and this study demonstrates that cyano-functionalization of BTI is a very effective strategy for developing polymers with deep-lying LUMOs for high-performance n-type organic electronic devices.

9.
Adv Mater ; 32(43): e2004183, 2020 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-32954584

RESUMEN

Narrow-bandgap polymer semiconductors are essential for advancing the development of organic solar cells. Here, a new narrow-bandgap polymer acceptor L14, featuring an acceptor-acceptor (A-A) type backbone, is synthesized by copolymerizing a dibrominated fused-ring electron acceptor (FREA) with distannylated bithiophene imide. Combining the advantages of both the FREA and the A-A polymer, L14 not only shows a narrow bandgap and high absorption coefficient, but also low-lying frontier molecular orbital (FMO) levels. Such FMO levels yield improved electron transfer character, but unexpectedly, without sacrificing open-circuit voltage (Voc ), which is attributed to a small nonradiative recombination loss (Eloss,nr ) of 0.22 eV. Benefiting from the improved photocurrent along with the high fill factor and Voc , an excellent efficiency of 14.3% is achieved, which is among the highest values for all-polymer solar cells (all-PSCs). The results demonstrate the superiority of narrow-bandgap A-A type polymers for improving all-PSC performance and pave a way toward developing high-performance polymer acceptors for all-PSCs.

10.
J Am Chem Soc ; 142(39): 16632-16643, 2020 Sep 30.
Artículo en Inglés | MEDLINE | ID: mdl-32852200

RESUMEN

As a key component in perovskite solar cells (PVSCs), hole-transporting materials (HTMs) have been extensively explored and studied. Aiming to meet the requirements for future commercialization of PVSCs, HTMs which can enable excellent device performance with low cost and eco-friendly processability are urgently needed but rarely reported. In this work, a traditional anchoring group (2-cyanoacrylic acid) widely used in molecules for dye-sensitized solar cells is incorporated into donor-acceptor-type HTMs to afford MPA-BT-CA, which enables effective regulation of the frontier molecular orbital energy levels, interfacial modification of an ITO electrode, efficient defect passivation toward the perovskite layer, and more importantly alcohol solubility. Consequently, inverted PVSCs with this low-cost HTM exhibit excellent device performance with a remarkable power conversion efficiency (PCE) of 21.24% and good long-term stability in ambient conditions. More encouragingly, when processing MPA-BT-CA films with the green solvent ethanol, the corresponding PVSCs also deliver a substantial PCE as high as 20.52% with negligible hysteresis. Such molecular design of anchoring group-based materials represents great progress for developing efficient HTMs which combine the advantages of low cost, eco-friendly processability, and high performance. We believe that such design strategy will pave a new path for the exploration of highly efficient HTMs applicable to commercialization of PVSCs.

11.
Dose Response ; 18(2): 1559325820920119, 2020.
Artículo en Inglés | MEDLINE | ID: mdl-32489336

RESUMEN

BACKGROUND: Although animal models have demonstrated dexmedetomidine (DEX) as neuroprotective in craniocerebral and subarachnoid injuries, but its role in humans remains to be elucidated. The objectives of the study were to compare plasma brain-derived neurotrophic factor (BDNF), cytokine, and superoxide dismutase levels of patients between those who received intraoperative DEX and those who received intraoperative normal saline (NSE) during peripheral or emergency neurologic surgeries. METHODS: Intra- and postoperative data of blood biomarkers and surgical outcomes of patients who underwent peripheral or emergency neurologic surgeries with mild-to-moderate traumatic brain injuries were analyzed retrospectively. Patients received intraoperative DEX group (n = 109) or NSE group (n = 116). RESULTS: At 15 minutes after intubation and before the operation, in the DEX group, plasma BDNF concentration decreased but remained much higher than the NSE group (P < .0001, q = 15.82). After 24 hours of surgeries, levels of cytokine were higher in the NSE group than the DEX group (P < .05 for all). Dexmedetomidine increased malondialdehyde (P < .0001) and superoxide dismutase (P < .0001) levels in DEX group. CONCLUSIONS: Intraoperative infusion of DEX may have a neuroprotective, anti-inflammatory, and antioxidant effects during peripheral or emergency neurologic surgeries. LEVEL OF EVIDENCE: III.

12.
Adv Mater ; 32(30): e2001476, 2020 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-32519429

RESUMEN

Compared to organic solar cells based on narrow-bandgap nonfullerene small-molecule acceptors, the performance of all-polymer solar cells (all-PSCs) lags much behind due to the lack of high-performance n-type polymers, which should have low-aligned frontier molecular orbital levels and narrow bandgap with broad and intense absorption extended to the near-infrared region. Herein, two novel polymer acceptors, DCNBT-TPC and DCNBT-TPIC, are synthesized with ultranarrow bandgaps (ultra-NBG) of 1.38 and 1.28 eV, respectively. When applied in transistors, both polymers show efficient charge transport with a highest electron mobility of 1.72 cm2 V-1 s-1 obtained for DCNBT-TPC. Blended with a polymer donor, PBDTTT-E-T, the resultant all-PSCs based on DCNBT-TPC and DCNBT-TPIC achieve remarkable power conversion efficiencies (PCEs) of 9.26% and 10.22% with short-circuit currents up to 19.44 and 22.52 mA cm-2 , respectively. This is the first example that a PCE of over 10% can be achieved using ultra-NBG polymer acceptors with a photoresponse reaching 950 nm in all-PSCs. These results demonstrate that ultra-NBG polymer acceptors, in line with nonfullerene small-molecule acceptors, are also available as a highly promising class of electron acceptors for maximizing device performance in all-PSCs.

13.
Angew Chem Int Ed Engl ; 59(34): 14449-14457, 2020 Aug 17.
Artículo en Inglés | MEDLINE | ID: mdl-32472603

RESUMEN

A distannylated electron-deficient bithiophene imide (BTI-Tin) monomer was synthesized and polymerized with imide-functionalized co-units to afford homopolymer PBTI and copolymer P(BTI-BTI2), both featuring an acceptor-acceptor backbone with high molecular weight. Both polymers exhibited excellent unipolar n-type character in transistors with electron mobility up to 2.60 cm2 V-1 s-1 . When applied as acceptor materials in all-polymer solar cells, PBTI and P(BTI-BTI2) achieved high power-conversion efficiency (PCE) of 6.67 % and 8.61 %, respectively. The PCE (6.67 %) of polymer PBTI, synthesized from the distannylated monomer, is much higher than that (0.14 %) of the same polymer PBTI*, synthesized from typical dibrominated monomer. The 8.61 % PCE of copolymer P(BTI-BTI2) is also higher than those (<1 %) of homopolymers synthesized from dibrominated monomers. The results demonstrate the success of BTI-Tin for accessing n-type polymers with greatly improved device performance.

14.
J Am Chem Soc ; 142(9): 4329-4340, 2020 Mar 04.
Artículo en Inglés | MEDLINE | ID: mdl-32048836

RESUMEN

Unpaired electrons of organic radicals can offer high electrical conductivity without doping, but they typically suffer from low stability. Herein, we report two organic diradicaloids based on quinoidal oligothiophene derivative (QOT), that is, BTICN and QTICN, with high stability and conductivity by employing imide-bridged fused molecular frameworks. The attachment of a strong electron-withdrawing imide group to the tetracyano-capped QOT backbones enables extremely deeply aligned LUMO levels (from -4.58 to -4.69 eV), cross-conjugated diradical characters, and remarkable ambient stabilities of the diradicaloids with half-lives > 60 days, which are among the highest for QOT diradicals and also the widely explored polyaromatic hydrocarbon (PAH)-based diradicals. Specifically, QTICN based on a tetrathiophene imide exhibits a cross-conjugation assisted self-doping in the film state as revealed by XPS and Raman studies. This property in combination with its ordered packing yields a high electrical conductivity of 0.34 S cm-1 for the QTICN films with substantial ambient stability, which is also among the highest values in organic radical-based undoped conductive materials reported to date. When used as an n-type thermoelectric material, QTICN shows a promising power factor of 1.52 uW m-1 K-2. Our results not only provide new insights into the electron conduction mechanism of the self-doped QOT diradicaloids but also demonstrate the great potential of fused quinoidal oligothiophene imides in developing stable diradicals and high-performance doping-free n-type conductive materials.

15.
Adv Sci (Weinh) ; 6(21): 1901773, 2019 Nov 06.
Artículo en Inglés | MEDLINE | ID: mdl-31728295

RESUMEN

Significant progress has been made in nonfullerene small molecule acceptors (NF-SMAs) that leads to a consistent increase of power conversion efficiency (PCE) of nonfullerene organic solar cells (NF-OSCs). To achieve better compatibility with high-performance NF-SMAs, the direction of molecular design for donor polymers is toward wide bandgap (WBG), tailored properties, and preferentially ecofriendly processability for device fabrication. Here, a weak acceptor unit, methyl 2,5-dibromo-4-fluorothiophene-3-carboxylate (FE-T), is synthesized and copolymerized with benzo[1,2-b:4,5-b']dithiophene (BDT) to afford a series of nonhalogenated solvent processable WBG polymers P1-P3 with a distinct side chain on FE-T. The incorporation of FE-T leads to polymers with a deep highest occupied molecular orbital (HOMO) level of -5.60-5.70 eV, a complementary absorption to NF-SMAs, and a planar molecular conformation. When combined with the narrow bandgap acceptor ITIC-Th, the solar cell based on P1 with the shortest methyl chain on FE-T achieves a PCE of 11.39% with a large V oc of 1.01 V and a J sc of 17.89 mA cm-2. Moreover, a PCE of 12.11% is attained for ternary cells based on WBG P1, narrow bandgap PTB7-Th, and acceptor IEICO-4F. These results demonstrate that the new FE-T is a highly promising acceptor unit to construct WBG polymers for efficient NF-OSCs.

16.
ACS Appl Mater Interfaces ; 11(39): 35924-35934, 2019 Oct 02.
Artículo en Inglés | MEDLINE | ID: mdl-31525945

RESUMEN

Imide functionalization is one of the most effective approaches to develop electron-deficient building blocks for constructing n-type organic semiconductors. Driven by the attractive properties of imide-functionalized dithienylbenzodiimide (TBDI) and the promising device performance of TBDI-based polymers, a novel acceptor with increased electron affinity, fluorinated dithienylbenzodiimide (TFBDI), was designed with the hydrogen replaced by fluorine on the benzene core, and the synthetic challenges associated with this highly electron-deficient fluorinated imide building block are successfully overcome. TFBDI showed suppressed frontier molecular orbital energy levels as compared with TBDI. Copolymerizing this new electron-withdrawing TBDI with various donor co-units afforded a series of n-type polymer semiconductors TFBDI-T, TFBDI-Se, and TFBDI-BSe. All these TFBDI-based polymers exhibited a lower-lying lowest unoccupied molecular orbital (LUMO) energy level than the polymer analogue without fluorine. When applied in organic thin-film transistors, three polymers showed unipolar electron transport with large on-current/off-current ratios (Ion/Ioff) of 105-107. Among them, the selenophene-based polymer TFBDI-Se with the deepest-positioned LUMO and optimal chain stacking exhibited the highest electron mobility of 0.30 cm2 V-1 s-1. This result demonstrates that the new TFBDI is a highly attractive electron-deficient unit for enabling n-type polymer semiconductors, and the fluorination of imide-functionalized arenes offers an effective approach to develop more electron-deficient building blocks in organic electronics.

17.
ACS Appl Mater Interfaces ; 11(36): 33505-33514, 2019 Sep 11.
Artículo en Inglés | MEDLINE | ID: mdl-31429258

RESUMEN

A novel nanomaterial, bismuth oxychloride nanoplates (BiOCl NPs), was first applied in organic solar cells (OSCs) as hole transporting layers (HTLs). It is worth noting that the BiOCl NPs can be facilely synthesized at ∼1/200 of the cost of the commercial PEDOT:PSS and well dissolved in green solvents. Different from the PEDOT:PSS interlayer, the deposition of BiOCl HTL is free of post-treatment at elevated temperature, which reduces device fabrication complexity. To demonstrate the universality of BiOCl in improving photovoltaic performance, OSCs containing various representative active layers were investigated. The power conversion efficiencies (PCEs) of the P3HT:PC61BM, PTB7-Th:PC71BM, and PM6:Y6-based OSCs with the BiOCl HTL boosted from 3.62, 8.78, and 15.63 to 4.24, 9.92, and 16.11%, respectively, compared to the PEDOT:PSS-based ones. It was found that the superior performances of the BiOCl-based OSCs are mainly attributed to the sufficient oxygen vacancies and improved interfacial contact. Moreover, the BiOCl-based OSCs show a much better stability than the cells with the PEDOT:PSS interfacial layer.

18.
Adv Mater ; 31(35): e1902781, 2019 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-31292989

RESUMEN

Hole-transporting materials (HTMs) play a critical role in realizing efficient and stable perovskite solar cells (PVSCs). Considering their capability of enabling PVSCs with good device reproducibility and long-term stability, high-performance dopant-free small-molecule HTMs (SM-HTMs) are greatly desired. However, such dopant-free SM-HTMs are highly elusive, limiting the current record efficiencies of inverted PVSCs to around 19%. Here, two novel donor-acceptor-type SM-HTMs (MPA-BTI and MPA-BTTI) are devised, which synergistically integrate several design principles for high-performance HTMs, and exhibit comparable optoelectronic properties but distinct molecular configuration and film properties. Consequently, the dopant-free MPA-BTTI-based inverted PVSCs achieve a remarkable efficiency of 21.17% with negligible hysteresis and superior thermal stability and long-term stability under illumination, which breaks the long-time standing bottleneck in the development of dopant-free SM-HTMs for highly efficient inverted PVSCs. Such a breakthrough is attributed to the well-aligned energy levels, appropriate hole mobility, and most importantly, the excellent film morphology of the MPA-BTTI. The results underscore the effectiveness of the design tactics, providing a new avenue for developing high-performance dopant-free SM-HTMs in PVSCs.

19.
J Phys Condens Matter ; 31(7): 075701, 2019 Feb 20.
Artículo en Inglés | MEDLINE | ID: mdl-30523806

RESUMEN

This study aims to characterize the size and shape dependent melting temperature of nanomaterials. Considering that surface atoms and interior atoms affect the melting of materials in different manners, we thus define an equivalent relationship between the contribution of surface atoms and interior atoms. Based on this definition, a criterion of melting is proposed through introducing a critical energy storage density of melting, the sum of the contribution of surface atoms and the interior atoms. According to the proposed criterion, a new theoretical model without any adjustable parameters is developed to characterize the size effect of melting temperatures of nanomaterials. The model predictions are in good agreement with the available experimental data or molecular dynamics simulations. This model uncovers the quantitative relationship between the melting temperature, size, atomic diameter and shape of nanomaterials. In addition, this model is extended to predict the size dependent glass transition temperatures of polymers. This study can help to better understand and characterize the size dependent melting temperatures of nanomaterials, as well as the size dependent glass transition temperatures of polymers.

20.
RSC Adv ; 8(62): 35724-35734, 2018 Oct 15.
Artículo en Inglés | MEDLINE | ID: mdl-35547934

RESUMEN

Head-to-head linked bithiophenes with planar backbones hold distinctive advantages for constructing organic semiconductors, such as good solubilizing capability, enabling narrow bandgap, and effective tuning of frontier molecular orbital (FMO) levels using minimal thiophene numbers. In order to realize planar backbone, alkoxy chains are typically installed on thiophene head positions, owing to the small van der Waals radius of oxygen atom and accompanying noncovalent S⋯O interaction. However, the strong electron donating alkoxy chains on the electron-rich thiophenes lead to elevated FMO levels, which are detrimental to material stability and device performance. Thus, a new design approach is needed to counterbalance the strong electron donating property of alkoxy chains to bring down the FMOs. In this study, we designed and synthesized a new head-to-head linked building block, 4-alkoxy-5-(3-alkylthiophen-2-yl)thiazole (TRTzOR), using an electron-deficient thiazole to replace the electron-rich thiophene. Compared to previously reported 3-alkoxy-3'-alkyl-2,2'-bithiophene (TRTOR), TRTzOR is a weaker electron donor, which considerably lowers FMOs and maintains planar backbone through the noncovalent S⋯O interaction. The new TRTzOR was copolymerized with benzothiadiazoles with distinct F numbers to yield a series of polymer semiconductors. Compared to TRTOR-based analogous polymers, these TRTzOR-based polymers have broader absorption up to 950 nm with lower-lying FMOs by 0.2-0.3 eV, and blending these polymers with PC71BM leads to polymer solar cells (PSCs) with improved open-circuit voltage (V oc) by ca. 0.1 V and a much smaller energy loss (E loss) as low as 0.59 eV. These results demonstrate that thiazole substitution is an effective approach to tune FMO levels for realizing higher V ocs in PSCs and the small E loss renders TRTzOR a promising building block for developing high-performance organic semiconductors.

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