Tuning Molecular Packing and Boosting Self-Assembling Properties via Ring Fusion Strategy in Naphthalimide-Based A-D-A Conjugated Systems.

Two fully fused acceptor-donor-acceptor (A-D-A) architecture conjugated derivatives (NPF and NCF) comprising an electron-withdrawing naphthalimide (NMI) and two different electron-donating cores, phenanthrene and carbazole, respectively, were conveniently synthesized by bismuth(III)-catalyzed selective cyclization of vinyl ethers. Compared with their corresponding single bond-linked A-D-A molecules NPS and NCS, both having a moderately twisted aromatic configuration, the ring fusion strategy leads to fully coplanar conjugated skeletons and greatly changes the electronic structures, photophysical properties, self-assembling behaviors, and molecular packing motifs. In particular, the naphthalimide/carbazole derivative NCF exhibits intriguing 2D brickwork packing and significantly enhanced self-assembling properties.

Manipulating Intramolecular Charge Transfer and Supramolecular Interaction in D-A-D Conjugated Systems by Regioisomerization.

Three new donor-acceptor-donor (D-A-D) architecture regioisomers comprising a large planar electron-withdrawing core tribenzo[a,c,i]phenazine and two identical electron-donating triphenylamines with different substitution patterns were designed and synthesized. Employing this regioisomerization strategy, the intramolecular charge-transfer interactions are effectively tuned and result in a significant bathochromic shift of photoluminescence maximum over 100 nm, which induces the corresponding emission band extending into the near-infrared region as well as giving a high solid-state quantum yield of 25%. Meanwhile, it is found that the supramolecular interactions of this series of regioisomers with planar electron-donor pyrene are greatly affected by the substitution pattern.

From π-conjugated macrocycles to heterocycloarenes based on benzo[2,1-b:3,4-b']dithiophene (BDTh): size- and geometry-dependent host-guest properties.

π-Conjugated macrocycles have been highly attractive due to their challenging synthesis, fascinating aesthetic structure and unique physical and chemical properties. Although some progress has been made in synthesis, the study of π-macrocycles with different structural characteristics and supramolecular interactions still faces major challenges. In this paper, two new single-bond linked macrocycles (MS-4T/MS-6T) were reported, and the corresponding vinyl-bridged heterocycloarenes (MF-4T/MF-6T) were synthesized by the periphery fusion strategy. Further studies have indicated that the structure of these four macrocycles is determined by both size and curvature, showing unique variations from nearly planar to bowl and then to saddle. Interestingly, the nearly planar MS-4T with a small size and the rigid saddle-shaped MF-6T show no obvious response to fullerenes C60 or C70, while the bowl-shaped MS-6T and MF-4T demonstrate a strong binding affinity towards fullerenes C60 and C70. What's more, two kinds of co-crystals with capsule-like configurations, MS-6T@C60 and MS-6T@C70, have been successfully obtained, among which the former shows a loose columnar arrangement while the latter displays a unique three-dimensional honeycomb arrangement that is extremely rare in supramolecular complexes. This work systematically studies the π-conjugated macrocycles and provides a new idea for the development of novel host-guest systems and further multifunctional applications.

Size-dependent properties and unusual reactivity of novel nonplanar heterocycloarenes.

The solution-phase synthesis of (hetero)cycloarenes with a well-defined size and geometric structure remains a challenging topic in organic chemistry and materials science. Herein, two novel nonplanar N,S-heterocycloarenes (PTZ1 and PTZ2) containing two/three alternate phenothiazine-co-phenanthrene units were conveniently synthesized. The smaller size heterocycloarene PTZ1 adopts a unique butterfly-shaped geometry and shows moderate supramolecular host-guest interactions with both fullerenes C60 and C70; whereas the higher homologue PTZ2 has a saddle-shaped conformation and demonstrates no obvious encapsulation with C60 or C70. Meanwhile, benefiting from the relatively ordered molecular packing, the thin film of PTZ1 behaved as a p-type semiconductor, while the more distorted PTZ2 does not display any field-effect characteristics. Particularly, upon the oxidation of heterocycloarene PTZ1 by Oxone, an unusual bis(sulfone-co-orthoquinone) product PTZ1-Oxi with an arc-shaped geometry is obtained and identified by single-crystal X-ray analysis. Our findings markedly expand the known chemistry of (hetero)cycloarenes and open a new path for their further functionalization.

BN-Embedded V-Shaped Polycyclic Aromatic Hydrocarbons Exhibiting Tunable Molecular Packing and Supramolecular Interactions.

Three novel BN-embedded V-shaped polycyclic aromatic hydrocarbons with different π-conjugation lengths were designed and successfully synthesized. Their single-crystal structures were confirmed by X-ray crystallographic analysis, and it is found that the molecular stacking structure can be effectively tuned by extending the length of π conjugation. Meanwhile, owing to the unique V-shaped molecular geometry, they exhibit moderate host-guest supramolecular interactions with both fullerenes C60 and C70.

Naphthalimide-based conjugated macrocycles possessing tunable self-assembly and supramolecular binding behaviours.

The special geometric configurations and optoelectronic properties of p-conjugated macrocycles have always been the focus of materials science. The incorporation of building moieties with different features into macrocycles can not only change their geometric configurations, but also realize the regulation of intramolecular charge transfer, which is expected to bring unusual performance in supramolecular chemistry and optoelectronic devices. Herein, four novel p-conjugated macrocycles based on typical electron acceptor units naphthalimide (NMI) with aryl or alkyl substitutions were reported. The different substitutions on NMI had greatly affected the self-assembly behaviours of these macrocycles. Alkyl substituted NP2b and NP3b showed obvious self-aggregation in solution, while similiar phenomenon was not found in aryl substituted macrocycles NP2a and NP3a, which can be attributed to the steric hindrance caused by rigid aryl groups that could affect the aggregation of macrocycles in solution. In addition, all the macrocycles exhibited supramolecular encapsulation with C70, in which the larger macrocycles NP3a and NP3b with twisted geometries showed stronger binding affinity towards C70 than the corresponding small-size macrocycles NP2a and NP2b with near-planar geometries. Our studies have greatly extended the family of macrocycles based on NMI, pointing out the direction for further supramolecular studies and applications on p-conjugated macrocycles.

Clinicopathological Characteristics and Influencing Factors of Renal Vascular Lesions in Anti-neutrophil Cytoplasmic Autoantibody-Related Renal Vasculitis.

The purpose of this study was to evaluate the clinicopathological features of different degrees of extraglomerular renal vascular lesions (RVLs) in patients with anti-neutrophil cytoplasmic antibody (ANCA)-associated renal vasculitis and explore their clinical determinants. This is a retrospective study of 186 patients with ANCA-associated renal vasculitis diagnosed at the First Affiliated Hospital of Zhengzhou University from January 2014 to April 2019. The patients who met the inclusion criteria were divided into non-renal RVLs, mild RVLs, moderate RVLs, and severe RVLs. It was found that there were significant differences in serum creatinine (SCR), estimated glomerular filtration rate (eGFR), erythrocyte sedimentation rate (ESR), high-density lipoprotein (HDL), systolic blood pressure (SBP), the prevalence rate of hypertension, the proportion of normal glomeruli, and the proportion of sclerotic glomeruli and interstitial fibrosis integral. SCR and ESR are independent risk factors for RVLs. The participants were followed up for 1 year, and the progression to end-stage renal disease (ESRD) and death was defined as endpoint events. We found that the survival rate of patients without RVLs was significantly higher than that of patients with RVLs and that the RVLs were an independent risk factor for ESRD or death. Early intervention in the progression of RVLs can improve the prognosis.

Clinicopathological characteristics and prognosis of hepatitis B associated membranous nephropathy and idiopathic membranous nephropathy complicated with hepatitis B virus infection.

The main objective of this study is to analyze the clinical and pathological features and prognosis of patients with Hepatitis B associated membranous nephropathy (HBV-MN) and idiopathic membranous nephropathy (IMN) complicated with hepatitis B virus (HBV) infection. This study will provide more basis for diagnosis and prognosis evaluation. A total of 50 patients with HBV-MN were included in this study. 56 IMN patients complicated with HBV infection diagnosed during the same period formed the control group. Parameters including blood routine, urine routine and plasma levels of albumin (ALB), serum creatinine (SCR), blood urea nitrogen (BUN), urea acid (UA), total cholesterol (T-CHO), triglycerides (TG), complement C3 and C4, glutamic pyruvic transaminase (ALT), glutamic pyruvic transaminase (AST), 24-h urinary protein quantification (24 h-TP), renal phospholipase A2 receptor (PLA2R) and HBV related markers during the hospitalization and outpatient follow-up study period were collected for all the patients. The proportion of male patients was high in both groups. The average age of the HBV-MN group was 37.2 ± 14.187 years old, it was younger compared with the IMN group (P = 0.003). Nephrotic syndrome was the major clinical manifestation among patients. There was no significant difference between the two groups in the levels of anemia, microscopic hematuria, renal dysfunction, liver dysfunction, liver cirrhosis. The level of serum C3 and C4 in the HBV-MN group was lower compared with the IMN group (P = 0.002, P = 0.014). In the HBV-MN group, serum HBV markers were negative in 6 (12%) patients, 4 patients (8%) were positive for PLA2R in serum, and 5 patients (10%) were positive for PLA2R in renal tissue. Stronger IgG1 and C1q and weaker IgG4 staining were found in HBV-MN group renal tissues (P = 0.003, P = 0.025, and P = 0.001, respectively). There were no statistical differences compared with serum and renal PLA2R between HBV-MN and IMN groups (P = 0.098, P = 0.109). During the 1-year follow-up, there was no significant difference in complete remission rate between the two groups (P = 0.7739). Renal biopsy is crucial to diagnose HBV-MN. IgG subtypes in the HBV-MN group were mainly IgG1 deposition, while those in IMN complicated with HBV infection group were mainly IgG4 deposition. When HBV-associated antigen and PLA2R are present in renal tissue, lower level of serum C3 and C4, high intensity of renal C1q and IgG1 is more supportive of HBV-MN. The positive of PLA2R in serum and renal tissue in differentiating HBV from IMN complicated with HBV infection remains to be discussed.

A cyclopenta-fused dibenzo[b,d]thiophene-co-phenanthrene macrocyclic tetraradicaloid.

A cyclopenta-fused macrocyclic tetraradicaloid, MC4-S, containing alternating phenanthrene (Phen) and dibenzo[b,d]thiophene (DBTh) units was synthesized and isolated in single-crystal form. Compared with its all-carbon isoelectronic structure, CPTP-M, the incorporation of two sulfur atoms leads to a smaller radical character and a larger singlet-triplet energy gap. X-ray crystallographic analysis reveals that the spin-spin coupling through the DBTh unit is stronger than that through the Phen moiety. In addition, the electron-rich sulfur atoms also raise the energies of both the HOMO and LUMO in MC4-S, but the overall optical and electronic energy gaps are close to that of the CPTP-M. MC4-S displays global anti-aromaticity according to the NMR measurements and theoretical calculations (NICS, ACID and 2D ICSS), with a 36π ring current circuit along the all-carbon periphery excluding the two sulphur atoms. Its dication becomes globally aromatic due to the existence of a dominant 34π-conjugation pathway. This study sheds some light on the effect of heteroatoms on the electronic properties of open-shell polyradicaloids.

Clinicopathological characteristics and outcomes of anti-neutrophil cytoplasmic autoantibody-related renal vasculitis with hyperuricemia: a retrospective case-control study.

The objective of the study was to evaluate the clinicopathological characteristics and investigate the clinical determinants of patient and renal survival in the first 12 months after diagnosis in anti-neutrophil cytoplasmic antibody (ANCA)-associated renal vasculitis (AAV) patients with hyperuricemia. This was a retrospective case-control study in patients with AAV-related renal injury in the First Affiliated Hospital of Zhengzhou University from January 2014 to April 2019. Patients who met the study criteria were divided into two groups: patients without hyperuricemia (n = 92) and patients with hyperuricemia (n = 55). Participants were followed-up for 12 months, and progressing to end-stage renal disease (ESRD) and death was treated as the endpoint event. We found that the level of serum creatinine was an independent risk factor for hyperuricemia, and the level of serum uric acid was an independent risk factors for renal survival and patient survival in ANCA-associated renal vasculitis patients. The crescents formation and the proportion of fibrous crescent likely contributed to severe clinical characteristics and renal pathological changes in ANCA-associated renal vasculitis patients with hyperuricemia. Hyperuricemia has an important influence on the progression of ANCA-associated renal vasculitis. A good control of serum uric acid may improve the prognosis.

Case Report: Glucocorticoids Combined With Immunosuppressant in the Treatment of Acromegaly Complicated With Focal Segmental Glomerulosclerosis.

Background: Acromegaly is a chronic disease caused by excessive secretion of growth hormone (GH), which circulates and stimulates the liver and body tissues to produce insulin-like growth factor type 1 (IGF-1). Experimental studies have shown that excessive secretion of GH is related to glomerular sclerosis, and elevated IGF-1 levels may be involved in the occurrence of glomerular hypertrophy. But relevant clinical cases are rare. Here, we reported a case of acromegaly complicated with focal segmental glomerulosclerosis (FSGS). Case Presentation: A 49-year-old man was admitted to our hospital because of acromegaly for more than 10 years and proteinuria for more than 3 years. Acromegaly was confirmed by contrast-enhanced magnetic resonance imaging, minimally invasive surgery and pathology. The results of renal biopsy showed FSGS-NOS (not otherwise specified) with ischemic renal injury and mesangial IgA deposition. One month after transnasal transsphenoidal space occupying resection, GH and urinary protein decreased significantly, and nephropathy was partially relieved. In the next 4 months, GH stabilized at the normal level, while urinary protein gradually increased. When the urinary protein increased to 4.2 g/d, the dosage of glucocorticoids increased to 20 mg/d, and tacrolimus 1 mg/d were added, and the urinary protein decreased again. However, when the urinary protein decreased to 0.43 g/d, the patient stopped taking glucocorticoids and tacrolimus, and the urinary protein increased to 2.85 g/d after 8 months, but the GH was still in the normal range. Conclusion: In this case, GH is partially involved in the formation of FSGS. Not only does surgery reduce the effects of GH, but low doses of glucocorticoids and immunosuppressant are effective in slowing the progression of kidney disease, at least in reducing urinary protein.