Cell softness regulates tumorigenicity and stemness of cancer cells.

Identifying and sorting highly tumorigenic and metastatic tumor cells from a heterogeneous cell population is a daunting challenge. Here, we show that microfluidic devices can be used to sort marker-based heterogeneous cancer stem cells (CSC) into mechanically stiff and soft subpopulations. The isolated soft tumor cells (< 400 Pa) but not the stiff ones (> 700 Pa) can form a tumor in immunocompetent mice with 100 cells per inoculation. Notably, only the soft, but not the stiff cells, isolated from CD133+ , ALDH+ , or side population CSCs, are able to form a tumor with only 100 cells in NOD-SCID or immunocompetent mice. The Wnt signaling protein BCL9L is upregulated in soft tumor cells and regulates their stemness and tumorigenicity. Clinically, BCL9L expression is correlated with a worse prognosis. Our findings suggest that the intrinsic softness is a unique marker of highly tumorigenic and metastatic tumor cells.

Analysis of ion transport properties of Glycine max HKT transporters and identifying a regulation of GmHKT1;1 by the non-functional GmHKT1;4.

The HKT transporter plays an important role for plants in response to salt stress, but the transport property of the soybean HKT transporters at the molecular level is still unclear. Here, using Xenopus oocyte as a heterologous expression system and two-electrode voltage-clamp technique, we identified four HKT transporters, GmHKT1;1, GmHKT1;2, GmHKT1;3, and GmHKT1;4, which all belong to type I subfamily, but having distinct ion transport properties. While GmHKT1;1, GmHKT1;2 and GmHKT1;3 function as Na+ transporters, GmHKT1;1 is less selective against K+ than the two other transporters. Astonishingly, GmHKT1;4, which lacks transmembrane segments and has no ion permeability, is significantly expressed, and its gene expression pattern is different from the other three GmHKTs under salt stress. Interestingly, GmHKT1;4 reduced the Na+/K+ currents mediated by GmHKT1;1. Further study showed that the transport ability of GmHKT1;1 regulated by GmHKT1;4 was related to the structural differences in the first intracellular domain and the fourth repeat domain. Overall, we have identified one unique GmHKT member, GmHKT1;4, which modulates the Na+ and K+ transport ability of GmHKT1;1 via direct interaction. Thus, we have revealed a new type of HKTs interaction model for altering their ion transport properties.

The G allele of SNP rs3922 reduces the binding affinity between IGF2BP3 and CXCR5 correlating with a lower antibody production.

Effective vaccines that function through humoral immunity seek to produce high-affinity antibodies. Our previous research identified the single-nucleotide polymorphism rs3922G in the 3'UTR of CXCR5 as being associated with nonresponsiveness to the hepatitis B vaccine. The differential expression of CXCR5 between the dark zone (DZ) and light zone (LZ) is critical for organizing the functional structure of the germinal center (GC). In this study, we report that the RNA-binding protein IGF2BP3 can bind to CXCR5 mRNA containing the rs3922 variant to promote its degradation via the nonsense-mediated mRNA decay pathway. Deficiency of IGF2BP3 leads to increased CXCR5 expression, which results in the disappearance of CXCR5 differential expression between DZ and LZ, disorganized GCs, aberrant somatic hypermutations, and reduced production of high-affinity antibodies. Furthermore, the affinity of IGF2BP3 for the rs3922G-containing sequence is lower than that for the rs3922A counterpart, which may explain the nonresponsiveness to the hepatitis B vaccination. Together, our findings suggest that IGF2BP3 plays a crucial role in the production of high-affinity antibodies in the GC by binding to the rs3922-containing sequence to regulate CXCR5 expression.

MicroRNA-202 safeguards meiotic progression by preventing premature SEPARASE-mediated REC8 cleavage.

MicroRNAs (miRNAs) are believed to play important roles in mammalian spermatogenesis but the in vivo functions of single miRNAs in this highly complex developmental process remain unclear. Here, we report that miR-202, a member of the let-7 family, plays an important role in spermatogenesis by phenotypic evaluation of miR-202 knockout (KO) mice. Loss of miR-202 results in spermatocyte apoptosis and perturbation of the zygonema-to-pachynema transition. Multiple processes during meiosis prophase I including synapsis and crossover formation are disrupted, and inter-sister chromatid synapses are detected. Moreover, we demonstrate that Separase mRNA is a miR-202 direct target and provides evidence that miR-202 upregulates REC8 by repressing Separase expression. Therefore, we have identified miR-202 as a new regulating noncoding gene that acts on the established SEPARASE-REC8 axis in meiosis.

A sensory neuron-specific long non-coding RNA reduces neuropathic pain by rescuing KCNN1 expression.

Nerve injury to peripheral somatosensory system causes refractory neuropathic pain. Maladaptive changes of gene expression in primary sensory neurons are considered molecular basis of this disorder. Long non-coding RNAs (lncRNAs) are key regulators of gene transcription; however, their significance in neuropathic pain remains largely elusive.Here, we reported a novel lncRNA, named sensory neuron-specific lncRNA (SS-lncRNA), for its expression exclusively in dorsal root ganglion (DRG) and trigeminal ganglion. SS-lncRNA was predominantly expressed in small DRG neurons and significantly downregulated due to a reduction of early B cell transcription factor 1 in injured DRG after nerve injury. Rescuing this downregulation reversed a decrease of the calcium-activated potassium channel subfamily N member 1 (KCNN1) in injured DRG and alleviated nerve injury-induced nociceptive hypersensitivity. Conversely, DRG downregulation of SS-lncRNA reduced the expression of KCNN1, decreased total potassium currents and afterhyperpolarization currents and increased excitability in DRG neurons and produced neuropathic pain symptoms.Mechanistically, downregulated SS-lncRNA resulted in the reductions of its binding to Kcnn1 promoter and heterogeneous nuclear ribonucleoprotein M (hnRNPM), consequent recruitment of less hnRNPM to the Kcnn1 promoter and silence of Kcnn1 gene transcription in injured DRG.These findings indicate that SS-lncRNA may relieve neuropathic pain through hnRNPM-mediated KCNN1 rescue in injured DRG and offer a novel therapeutic strategy specific for this disorder.

Dietary rutin improves the antidiarrheal capacity of weaned piglets by improving intestinal barrier function, antioxidant capacity and cecal microbiota composition.

BACKGROUND: Early weaning is prone to damage intestinal barrier function, resulting in diarrhea, whereas rutin, as a natural flavonoid with multiple biological functions, shows potential in piglets. Therefore, the effects of dietary rutin on growth, antidiarrheal, barrier function, antioxidant status and cecal microbiota of weaned piglets were investigated with the control group (CON) (basal diet) and Rutin (basal diet+500 mg kg-1 rutin) groups fed for 14 days. RESULTS: The results showed that dietary 500 mg kg-1 rutin significantly decreased diarrhea index, serum diamine oxidase activity and total aerobic bacterial population in mesenteric lymph nodes, whereas it significantly increased the gain-to-feed ratio (G:F) and serum growth hormone content, jejunal villus height and villus height to crypt depth ratio, and also enhanced jejunal claudin-1 and zonula occludens-1 mRNA and protein expression. Meanwhile, dietary rutin significantly decreased inflammation-associated mRNA expression, malondialdehyde (MDA) content, swollen mitochondrial number and mitochondrial area in the jejunum, whereas it increased the total superoxide dismutase (T-SOD) and glutathione peroxidase activities and activated the Nrf2 signaling pathway. Moreover, dietary rutin significantly increased Firmicutes abundance and decreased Campylobacterota abundance, which were closely associated with the decreased diarrhea index and MDA content or increased Claudin-1 expression and T-SOD activity. CONCLUSION: Dietary 500 mg kg-1 rutin increased G:F by improving intestinal morphology, and alleviated diarrhea by enhancing intestinal barrier, which might be associated with the enhanced antioxidant capacity via activating the Nrf2/Keap1 signaling pathway and the improved cecal microbial composition in weaned piglets. © 2024 Society of Chemical Industry.

Diffusion MRI is valuable in brainstem glioma genotyping with quantitative measurements of white matter tracts.

OBJECTIVES: To investigate the value of diffusion MRI (dMRI) in H3K27M genotyping of brainstem glioma (BSG). METHODS: A primary cohort of BSG patients with dMRI data (b = 0, 1000 and 2000 s/mm2) and H3K27M mutation information were included. A total of 13 diffusion tensor and kurtosis imaging (DTI; DKI) metrics were calculated, then 17 whole-tumor histogram features and 29 along-tract white matter (WM) microstructural measurements were extracted from each metric and assessed within genotypes. After feature selection through univariate analysis and the least absolute shrinkage and selection operator method, multivariate logistic regression was used to build dMRI-derived genotyping models based on retained tumor and WM features separately and jointly. Model performances were tested using ROC curves and compared by the DeLong approach. A nomogram incorporating the best-performing dMRI model and clinical variables was generated by multivariate logistic regression and validated in an independent cohort of 27 BSG patients. RESULTS: At total of 117 patients (80 H3K27M-mutant) were included in the primary cohort. In total, 29 tumor histogram features and 41 WM tract measurements were selected for subsequent genotyping model construction. Incorporating WM tract measurements significantly improved diagnostic performances (p < 0.05). The model incorporating tumor and WM features from both DKI and DTI metrics showed the best performance (AUC = 0.9311). The nomogram combining this dMRI model and clinical variables achieved AUCs of 0.9321 and 0.8951 in the primary and validation cohort respectively. CONCLUSIONS: dMRI is valuable in BSG genotyping. Tumor diffusion histogram features are useful in genotyping, and WM tract measurements are more valuable in improving genotyping performance. CLINICAL RELEVANCE STATEMENT: This study found that diffusion MRI is valuable in predicting H3K27M mutation in brainstem gliomas, which is helpful to realize the noninvasive detection of brainstem glioma genotypes and improve the diagnosis of brainstem glioma. KEY POINTS: • Diffusion MRI has significant value in brainstem glioma H3K27M genotyping, and models with satisfactory performances were built. • Whole-tumor diffusion histogram features are useful in H3K27M genotyping, and quantitative measurements of white matter tracts are valuable as they have the potential to improve model performance. • The model combining the most discriminative diffusion MRI model and clinical variables can help make clinical decision.

Viewpoint-dependent highlight depiction with microdisparity for autostereoscopic displays.

The rendering of specular highlights is a critical aspect of 3D rendering on autostereoscopic displays. However, the conventional highlight rendering techniques on autostereoscopic displays result in depth conflicts between highlights and diffuse surfaces. To address this issue, we propose a viewpoint-dependent highlight depiction method with head tracking, which incorporates microdisparity of highlights in binocular parallax and preserves the motion parallax of highlights. Our method was found to outperform physical highlight depiction and highlight depiction with microdisparity in terms of depth perception and realism, as demonstrated by experimental results. The proposed approach offers a promising alternative to traditional physical highlights on autostereoscopic displays, particularly in applications that require accurate depth perception.

Amplified Drug Delivery System with a Pair of Master Keys Triggering Precise Drug Release for Chemo-Photothermal Therapy.

A versatile drug delivery system (DDS) enabling highly effective and targeting oncotherapy has always been of great significance in medical research. In the development of a stimuli-responsive DDS, compared with a single-factor stimulation DDS, a multifactor activation DDS has higher therapeutic specificity between diseased and normal tissue, but there are challenges in drug-release efficiency and united targeting cancer therapy. Herein, a novel dual-microRNA (dual-miRNA)-mediated 1:N-amplified DDS is fabricated. The gold nanocage (AuNC) was synthesized and used as a carrier. A DNA bridge motif as a nanolock (DNA bridge nanolock) was designed and modified on the surface of AuNCs, which could seal the holes of AuNCs. Using the dual-miRNAs as a pair of master keys, through DNA strand migration and DNAzyme self-assembly, a cell endogenous substance Mg2+-dependent DNAzyme cyclic shear reaction could perform the function of the master keys to open multiple locks for the enhanced release of doxorubicin from the AuNCs. In addition, under near-infrared irradiation, via absorption of light and heat release, the AuNC is activated to perform the function of photothermal therapy. Thereby, the system achieves precise chemo-photothermal therapy. Using the in vitro and in vivo anti-tumor analysis, the DDS could be proved to present a novel design of enhanced and targeted drug-release system for highly effective cancer therapy.

The transcription factor SOX30 is a key regulator of mouse spermiogenesis.

The postmeiotic development of male germ cells, also known as spermiogenesis, features the coordinated expression of a large number of spermatid-specific genes. However, only a limited number of key transcription factors have been identified and the underlying regulatory mechanisms remain largely unknown. Here, we report that SOX30, the most-divergent member of the Sry-related high-motility group box (SOX) family of transcription factors, is essential for mouse spermiogenesis. The SOX30 protein was predominantly expressed in spermatids, while its transcription was regulated by retinoic acid and by MYBL1 before and during meiosis. Sox30 knockout mice arrested spermiogenesis at step 3 round spermatids, which underwent apoptosis and abnormal chromocenter formation. We also determined that SOX30 regulated the expression of hundreds of spermatid-specific protein-coding and long non-coding RNA genes. SOX30 bound to the proximal promoter of its own gene and activated its transcription. These results reveal SOX30 as a novel key regulator of spermiogenesis that regulates its own transcription to enforce and activate this meiotic regulatory pathway.

Tapered Mach-Zehnder interferometer based on PbS quantum dots modified by polymers for copper ion sensing.

An optical fiber interferometer coated with PbS quantum dots (QDs) was developed for copper ion (${{\rm{Cu}}^{2 +}}$) detection. The QDs were modified by a multifunctional copolymer that enabled QD surface ligation, dispersion, and coordination with ${{\rm{Cu}}^{2 +}}$. ${{\rm{Cu}}^{2 +}}$ coordination with the polymer induced changes in the surrounding refractive index of the interferometer. The sensor was highly selective for ${{\rm{Cu}}^{2 +}}$ and showed a linear detection range of 0-1000 µM with a limit of detection of 2.20 µM in both aqueous and biological solutions.

Extended Right Thoracic Approach Compared With Limited Left Thoracic Approach for Patients With Middle and Lower Esophageal Squamous Cell Carcinoma: Three-year Survival of a Prospective, Randomized, Open-label Trial.

OBJECTIVE: To investigate whether survival is improved by using the right thoracic approach (extended lymphadenectomy) compared with the left thoracic approach (limited lymphadenectomy) for esophageal cancer. BACKGROUND: The optimal surgical technique for esophageal cancer remains unclear. METHODS: Between May 2010 and July 2012, 300 patients with middle and lower thoracic esophageal carcinoma were randomized to receive esophagectomy through either the right or left thoracic approach. Of these, 286 patients with squamous cell carcinoma determined by postoperative pathology were included in this analysis. Disease-free survival (DFS) and overall survival (OS) were compared between the right (n = 146) and left thoracic groups (n = 140). RESULTS: The median follow-up was 55.9 months [95% confidence interval (CI): 53.1-58.6]. The 3-year DFS rates were 62% and 52% in the right and left thoracic arms, respectively [hazard ratio (HR) 0.709; 95% CI, 0.506-0.995; P = 0.047, log-rank test]. The 3-year OS rates were 74% and 60%, respectively (HR, 0.663; 95% CI, 0.457-0.961; P = 0.029). Subgroup analyses revealed longer DFS in the right thoracic arm (vs left thoracic arm) in patients with lymph node involvement (HR, 0.632; 95% CI, 0.412-0.969, P = 0.034), but not in patients without lymph node involvement (HR, 0.757; 95% CI, 0.434-1.320, P = 0.325), and in patients with R1-2 resection margins (HR, 0.495; 95% CI, 0.290-0.848, P = 0.009), but not R0 margins (HR, 0.944; 95% CI, 0.603-1.477, P = 0.801). CONCLUSIONS: Compared with the left thoracic approach, the right thoracic approach associated with increased DFS and OS in esophageal squamous cell carcinoma patients, particularly in those with lymph node involvement and/or R1-2 resection margins.

3D Visualization and Augmented Reality for Orthopedics.

Augmented reality (AR) techniques play an important role in the field of minimally invasive surgery for orthopedics. AR can improve the hand-eye coordination by providing surgeons with the merged surgical scene, which enables surgeons to perform surgical operations more easily. To display the navigation information in the AR scene, medical image processing and three-dimensional (3D) visualization of the important anatomical structures are required. As a promising 3D display technique, integral videography (IV) can produce an autostereoscopic image with full parallax and continuous viewing points. Moreover, IV-based 3D AR navigation technique is proposed to present intuitive scene and has been applied in orthopedics, including oral surgery and spine surgery. The accurate patient-image registration, as well as the real-time target tracking for surgical tools and the patient, can be achieved. This paper overviews IV-based AR navigation and the applications in orthopedics, discusses the infrastructure required for successful implementation of IV-based approaches, and outlines the challenges that must be overcome for IV-based AR navigation to advance further development.

Augmented reality technology for preoperative planning and intraoperative navigation during hepatobiliary surgery: A review of current methods.

BACKGROUND: Augmented reality (AR) technology is used to reconstruct three-dimensional (3D) images of hepatic and biliary structures from computed tomography and magnetic resonance imaging data, and to superimpose the virtual images onto a view of the surgical field. In liver surgery, these superimposed virtual images help the surgeon to visualize intrahepatic structures and therefore, to operate precisely and to improve clinical outcomes. DATA SOURCES: The keywords "augmented reality", "liver", "laparoscopic" and "hepatectomy" were used for searching publications in the PubMed database. The primary source of literatures was from peer-reviewed journals up to December 2016. Additional articles were identified by manual search of references found in the key articles. RESULTS: In general, AR technology mainly includes 3D reconstruction, display, registration as well as tracking techniques and has recently been adopted gradually for liver surgeries including laparoscopy and laparotomy with video-based AR assisted laparoscopic resection as the main technical application. By applying AR technology, blood vessels and tumor structures in the liver can be displayed during surgery, which permits precise navigation during complex surgical procedures. Liver transformation and registration errors during surgery were the main factors that limit the application of AR technology. CONCLUSIONS: With recent advances, AR technologies have the potential to improve hepatobiliary surgical procedures. However, additional clinical studies will be required to evaluate AR as a tool for reducing postoperative morbidity and mortality and for the improvement of long-term clinical outcomes. Future research is needed in the fusion of multiple imaging modalities, improving biomechanical liver modeling, and enhancing image data processing and tracking technologies to increase the accuracy of current AR methods.

Choledochoscopic Examination of a 3-Dimensional Printing Model Using Augmented Reality Techniques: A Preliminary Proof of Concept Study.

BACKGROUND: We applied augmented reality (AR) techniques to flexible choledochoscopy examinations. METHODS: Enhanced computed tomography data of a patient with intrahepatic and extrahepatic biliary duct dilatation were collected to generate a hollow, 3-dimensional (3D) model of the biliary tree by 3D printing. The 3D printed model was placed in an opaque box. An electromagnetic (EM) sensor was internally installed in the choledochoscope instrument channel for tracking its movements through the passages of the 3D printed model, and an AR navigation platform was built using image overlay display. The porta hepatis was used as the reference marker with rigid image registration. The trajectories of the choledochoscope and the EM sensor were observed and recorded using the operator interface of the choledochoscope. RESULTS: Training choledochoscopy was performed on the 3D printed model. The choledochoscope was guided into the left and right hepatic ducts, the right anterior hepatic duct, the bile ducts of segment 8, the hepatic duct in subsegment 8, the right posterior hepatic duct, and the left and the right bile ducts of the caudate lobe. Although stability in tracking was less than ideal, the virtual choledochoscope images and EM sensor tracking were effective for navigation. CONCLUSIONS: AR techniques can be used to assist navigation in choledochoscopy examinations in bile duct models. Further research is needed to determine its benefits in clinical settings.

Surgical Outcomes of Isolated Malignant Pulmonary Nodules in Patients with a History of Breast Cancer.

BACKGROUND: The role of surgery for isolated malignant pulmonary nodules in breast cancer patients remains unclear. METHODS: A total of 1286 consecutive breast cancer patients with pulmonary nodules detected by thoracic computed tomography (CT) or positron emission tomography (PET)/CT scan at Shanghai Cancer Center, Fudan University, were reviewed. Overall, 147 breast cancer patients with isolated malignant pulmonary nodules receiving surgery and/or chemotherapy were enrolled in the study. Patients were classified into three groups: patients with primary lung cancer (PLC) receiving surgery (Group 1), patients with lung metastasis receiving surgery (Group 2), and patients with lung metastasis receiving chemotherapy (Group 3). Survival outcomes, including overall survival (OS) and progression-free survival (PFS), were analyzed for patients in all three groups, and prognostic factors for PFS for patients with pulmonary metastasis were evaluated. RESULTS: Patients with PLC receiving surgery had better survival outcomes, including OS and PFS, than patients with lung metastases who received surgical resection. Breast cancer patients with solitary lung metastasis who received metastasectomy had a significantly better PFS than those who did not; however, no statistically significant difference in OS was observed between the two groups. A multivariate analysis conducted in patients with isolated metastatic breast cancer showed that surgery was an independent factor for better PFS. CONCLUSIONS: Surgery should be considered a valid option for the diagnosis and treatment of breast cancer patients presenting with isolated malignant lung nodules.

Characteristics and clinical significance of recurrent laryngeal nerve lymph node metastasis in esophageal squamous cell carcinoma.

PURPOSE: The recurrent laryngeal nerve lymph nodes (RLN LNs) are among the most common metastatic sites in esophageal cancer, and the dissection of these lymph nodes (LNs) is considered beneficial. The purpose of this study was to evaluate the characteristics of RLN LN metastases from esophageal squamous cell carcinoma, and the effects of these metastases on the prognosis of patients. In addition, we aimed to determine the reasonable range of dissection of regional LNs. METHODS: The clinical data from 348 patients who underwent resection for esophageal carcinoma were retrospectively analyzed. RESULTS: Recurrent laryngeal nerve palsy occurred in 37.6% of the patients. In a subgroup of patients with lower esophageal tumors, cervical LN metastases were significantly more common in patients with positive rather than negative RLN LNs. The primary tumor site, tumor differentiation, and tumor invasion depth were factors that significantly influenced RLN LN metastasis. Multivariate analysis revealed that RLN LN metastasis was a significant factor associated with overall survival (OS) and disease-free survival (DFS) (p<0.001). CONCLUSION: Metastasis to RLN LNs is a reliable indicator of cervical LN metastasis in middle/lower thoracic esophageal cancer. RLN LN metastasis may act as a prognostic indicator for patients with esophageal squamous cell carcinoma.

Copper ion salts of arylthiotetrathiafulvalenes: synthesis, structure diversity and magnetic properties.

The combination of CuBr2 and arylthio-substituted tetrathiafulvalene derivatives (1-7) results in a series of charge-transfer (CT) complexes. Crystallographic studies indicate that the anions in the complexes, which are derived from CuBr2, show diverse configurations including linear [Cu(I)Br2](-), tetrahedral [Cu(II)Br4](2-), planar [Cu(II)2Br6](2-), and coexistence of planar [Cu(II)Br4](2-) and tetrahedral [Cu(II)Br3](-) ions. On the other hand, the TTFs show either radical cation or dication states that depend on their redox potentials. The central TTF framework on most of TTFs is nearly planar despite the charge on them, whereas the two dithiole rings on molecule 4 in complex 4·CuBr4 are significantly twisted with a dihedral angle of 38.3°. The magnetic properties of the complexes were elucidated. The temperature-dependent magnetic susceptibility of complex 5·Cu2Br6 shows the singlet-triplet transition with coupling constant J = -248 K, and that of 3·(CuBr4)0.5·CuBr3·THF shows the abrupt change at 270 K caused by the modulation of intermolecular interactions. The thermo variation of magnetic susceptibility for the other complexes follows the Curie-Weiss law, indicating the weak antiferromagnetic interaction at low temperature.

Donor-acceptor type co-crystals of arylthio-substituted tetrathiafulvalenes and fullerenes.

A series of donor-acceptor type co-crystals of fullerene (as the acceptor) and arylthio-substituted tetrathiafulvalene derivatives (Ar-S-TTF, as the donor) were prepared and their structural features were thoroughly investigated. The formation of co-crystals relies on the flexibility of Ar-S-TTF and the size matches between Ar-S-TTF and fullerene. Regarding their compositions, the studied co-crystals can be divided into two types, where types I and II have donor:acceptor ratios of 1:1 and 1:2, respectively. Multiple intermolecular interactions are observed between the donor and acceptor, which act to stabilize the structures of the resulting co-crystals. In the type I co-crystals, the fullerene molecule is surrounded by four Ar-S-TTF molecules, that is, two Ar-S-TTF molecules form a sandwich structure with one fullerene molecule and the other two Ar-S-TTF molecules interact with the fullerene molecule along their lateral axes. In the type II co-crystals, one fullerene molecule has the donor-acceptor mode similar to that in type I, whereas the other fullerene molecule is substantially surrounded by the aryl groups on Ar-S-TTF molecules and the solvent molecules.

Decorating tetrathiafulvalene (TTF) with fluorinated phenyls through sulfur bridges: facile synthesis, properties, and aggregation through fluorine interactions.

Tetrathiafulvalene derivatives (TTF1-TTF9) bearing fluorinated phenyl groups attached through the sulfur bridges have been synthesized by employing a copper-mediated C-S coupling reaction of C6 H5-x Fx I (x=1, 2, 5) and a zinc-thiolate complex, (TBA)2 [Zn(DMIT)2 ] (TBA=tetrabutyl ammonium, DMIT=1,3-dithiole-2-thione-4,5-dithiolate), as the key step. Particularly, the selective synthesis of C6 F5 -substituted (TTF8) and C6 F4 -fused (TTF9) TTFs from C6 F5 I is disclosed. The physicochemical properties and crystal structures of these TTFs are fully investigated by UV/Vis absorption spectra, cyclic voltammetry, molecular orbital calculation, and single-crystal X-ray diffraction. The exchange of hydrogen versus fluorine on the peripheral phenyl groups show a notable influence on both the electronic and crystallographic natures of the resulting TTFs: 1) lowering both the HOMO and the LUMO energy levels, 2) modulating the electrochemical properties by regioselective and/or the degree of fluorination, 3) enhancing the driving forces of stacking by multiple fluorine interactions (F⋅⋅⋅S, CF⋅⋅⋅π/πF , CF⋅⋅⋅FC, and CF⋅⋅⋅H). This work indicates that the decoration with fluorinated phenyls holds promise to produce functional TTFs with novel electronic and aggregation features.