Impacts of inflammatory cytokines on depression: a cohort study.

BACKGROUND: Inflammatory factors are associated with depression. We seek to investigate the correlation between inflammatory cytokines and prognosis of depression or suicidal ideation and behavior at 3 months in depression patients. METHODS: Eighty-two depressed outpatients were recruited and treated as usual. Plasma cytokines were measured at baseline. Patients were followed up with Patient Health Questionnaire-9 and suicidal ideation and behavior according to the item 3 of Hamilton depression scale for 3 months. RESULTS: Compared to the depression patients with low level of interleukin-1ß, the high one had severe depressive symptoms at month 2 and 3 (B 0.92, P < 0.01; B 0.86, P = 0.02; respectively). The incidence of suicidal ideation or behavior was 18.3% at 3 months. Depression patients with high levels of tumor necrosis factor-α showed high risk of suicidal ideation and behavior than the low one (OR 2.16, 95% CI 1.00-4.65, P = 0.04). CONCLUSIONS: High levels of interleukin-1ß and tumor necrosis factor-α were predictive of middle-term severe depressive symptoms and suicidal ideation and behavior respectively.

Halogen-regulating induced reversible high-temperature dielectric and thermal transitions in novel layered organic-inorganic hybrid semiconducting crystals.

Organic-inorganic hybrid metal halides for high-temperature phase transition have become increasingly popular owing to their wide operating temperature range in practical applications, e.g., energy storage, permittivity switches and opto-electronic devices. This paper describes the subtle assembly of two new hybrid perovskite crystals, [Cl-C6H4-(CH2)2NH3]2CdX4 (X = Br 1; Cl 2), undergoing high-T reversible phase transformations around 335 K/356 K. Differential scanning calorimetry (DSC), differential thermal analysis (DTA) and VT PXRD tests uncover their reversible first-order phase transition behaviors. Furthermore, the compounds exhibit switchable dielectricity near T, making them potential dielectric switching materials. Hirshfeld surface analysis well discloses a distinct difference in hydrogen-bonding interaction between 1 and 2. UV spectra and computational analysis demonstrate that the compounds are a type of direct-band-gap semiconductor. This research will contribute an effective approach to the structure and development of multifunctional molecular hybrid crystals.

High-Temperature Ferroelasticity and Photoluminescence in a 2D Monolayer Perovskite Compound: (C5NH8Br)2PbBr4.

Hybrid organic-inorganic perovskites (HOIPs) have attracted much attention due to their excellent properties and easy synthesis. As far as we know, most documented ferroelastics mainly focus on the 3D (three-dimensional) perovskites, the 2D monolayer perovskite ferroelastics are rarely reported before. In this work, we synthesized a 2D lead-based perovskite (C5NH13Br)2PbBr4 (1) (C5NH13Br = 5-bromoamylamine cation) by introducing flexible chain organic cations. The evolution of ferroelastic domains observed by a polarized light microscope confirms that compound 1 undergoes a ferroelastic phase transition at 392/384 K. In addition, its direct band gap is 2.877 eV. Interestingly, the material emits an attractive blue light (quantum yield 5.06%) under UV light. Three structural descriptors are introduced to quantitatively analyze the relationship between structural distortion and the shape of emission peak. This work provides a way to design multifunctional perovskite-type materials.

1D Chiral Lead Bromide Perovskite with Superior Second-Order Optical Nonlinearity, Photoluminescence, and High-Temperature Reversible Phase Transition.

Multifunctional materials are an attractive research area. Organic-inorganic hybrid perovskites are widely used in the design of these materials due to their rich properties and flexible composition. It is easy to obtain more photoelectric properties by introducing chiral groups as ligands. In this work, we synthesized chiral one-dimensional organic-inorganic hybrid perovskites, namely (R/S-3-HP)PbBr3 (1R/1S) (3-HP=3-hydroxy-piperidine). The enantiomer compounds undergo reversible phase transition at 349/336 K. Under the excitation light of 339 nm, 1R and 1S have a wide emission peak at 635 nm, showing orange light. In addition, the indirect bandgap is 3.29 eV and the SHG intensity is comparable to that of KDP. This work provides a way to design multifunctional chiral perovskite materials.

Preferential subcortical collateral projections of pedunculopontine nucleus-targeting cortical pyramidal neurons revealed by brain-wide single fiber tracing.

The pedunculopontine nucleus (PPN) is a heterogeneous midbrain structure involved in various brain functions, such as motor control, learning, reward, and sleep. Previous studies using conventional tracers have shown that the PPN receives extensive afferent inputs from various cortical areas. To examine how these cortical axons make collateral projections to other subcortical areas, we used a dual-viral injection strategy to sparsely label PPN-targeting cortical pyramidal neurons in CaMKIIα-Cre transgenic mice. Using a high-speed volumetric imaging with on-the-fly-scan and Readout (VISoR) technique, we visualized brain-wide axonal projections of individual PPN-targeting neurons from several cortical areas, including the prelimbic region (PL), anterior cingulate area (ACA) and secondary motor cortex (MOs). We found that each PPN-projecting neuron had a unique profile of collateralization, with some subcortical areas being preferential targets. In particular, PPN-projecting neurons from all three traced cortical areas exhibited common preferential collateralization to several nuclei, with most neurons targeting the striatum (STR), lateral hypothalamic area (LHA) and periaqueductal gray (PAG), and a substantial portion of neurons also targeting the zona incerta (ZI), median raphe nucleus (MRN) and substantia nigra pars reticulata (SNr). Meanwhile, very specific collateralization patterns were found for other nuclei, including the intermediate reticular nucleus (IRN), parvicellular reticular nucleus (PARN) and gigantocellular reticular nucleus (GRN), which receive collateral inputs almost exclusively from the MOs. These observations provide potential anatomical mechanisms for cortical neurons to coordinate the PPN with other subcortical areas in performing different physiological functions.

Impact of Persistent Poor Sleep Quality on Post-Stroke Anxiety and Depression: A National Prospective Clinical Registry Study.

Purpose: The impact of poor sleep quality after stroke, especially persistent poor sleep quality, on poststroke anxiety and depression is unclear. We seek to investigate the impact of baseline and persistent poor sleep quality on short-term poststroke anxiety and depression. Patients and Methods: Data were analyzed for 1619 patients with acute ischemic stroke from the Impairment of Cognition and Sleep after Acute Ischemic Stroke or Transient Ischemic Attack in Chinese Patients study (ICONS). The sleep quality was assessed at 2 weeks and 3 months using the Pittsburgh Sleep Quality Index scale (PSQI). Poor sleep quality was defined as a PSQI score of >5, and persistent poor sleep quality was defined as a PSQI score of >5 at each time point. Patients were divided into three groups according to the quality of sleep: good sleep quality, baseline poor sleep quality and persistent poor sleep quality. Patient Health Questionnaire-9 (PHQ-9), General Anxiety Disorder-7 scale (GAD-7), and Modified Rankin Scale (mRS) at 3 months after stroke were taken as the study outcomes. Results: Persistent poor sleep quality was present in 70.2% of patients after stroke. Compared to those with good sleep quality, patients with baseline poor sleep quality did not show significant differences in disability, anxiety and depression. However, patients with persistent poor sleep were at increased risk of depression (odds ratio, OR 3.04, 95% confidence interval, CI 1.66-5.57, P < 0.01) and anxiety (OR 3.20, 95% CI 1.42-7.19, P < 0.01) at 3 months after stroke. Persistent poor sleep quality was not identified as a risk factor for functional disability at 3 months. Conclusion: Patients with persistent poor sleep quality are at added risks for depression and anxiety after stroke.

Two Manganese(II)-Based Hybrid Multifunctional Phase Transition Materials with Strong Photoluminescence, High Quantum Yield, and Switchable Dielectric Properties: (C6NH16)2MnBr4 and (C7NH18)2MnBr4.

Multifunctional materials have always been an attractive research area, but how to combine multiple excellent properties in one compound remains a considerable challenge. Organic-inorganic hybrid compounds are widely used in the design of such materials due to their rich properties and flexible assembly. Herein, two new manganese(II)-based organic-inorganic hybrid compounds, (C6NH16)2MnBr4 (1) and (C7NH18)2MnBr4 (2), are prepared by the solution method. Compounds 1 and 2 both emit extremely strong green light under UV excitation, with high quantum yields of 45.93 and 50.98%, respectively. In addition, reversible solid-state phase transitions and obvious switchable dielectric properties are shown at 378/366 and 361/352 K, respectively. The coexistence of the dual stimulus-response characteristics of temperature and light in compounds 1 and 2 opens a new path for exploring more multifunctional phase transition materials.

Regulating Reversible Phase Transition Behaviors by Poly-H/F Substitution in Hybrid Perovskite-Like 2[CH2FCH2NH3]·[CdCl4].

The molecular design and regulation has shown bright future for constructing smart molecular materials such as ferroelectrics, dielectric switches, electro-optic effect, and so forth. Here, by poly-H/F substitution in a simple organic-inorganic hybrid 2[CH2FCH2NH3]·[CdCl4], 1 (CH2FCH2NH3 = fluorine ethylamine cation), we obtained two novel hybrids, namely, 2[CHF2CH2NH3]·[CdCl4], 2 (CHF2CH2NH3 = 2,2'-difluorine ethylamine cation) and 2[CF3CH2NH3]·[CdCl4], 3 (CF3CH2NH3 = 2,2',2″-trifluorine ethylamine cation). Further investigations show that compounds 1, 2, and 3 experience solid reversible phase transitions with temperatures at 294, 319, and 329 K respectively. These unique phase transitions were confirmed by their remarkable dielectric and heat anomalies around the phase transition temperatures. X-ray single-crystal diffraction analyses before and after the phase transitions show that the order-disorder motions of F atoms and the twist motions from the 2D [CdCl4]2- framework lead to these solid reversible phase transitions. Also, the Hirshfeld surface calculation of compounds 1, 2, and 3 suggests that the increasing ratio of the F···F interaction from the intermolecular interaction makes a major contribution for the substantial increase of their phase transition temperatures.

Designing and Constructing a High-Temperature Molecular Ferroelectric by Anion and Cation Replacement in a Simple Crown Ether Clathrate.

Molecular ferroelectrics have displayed a promising future since they are light-weight, flexible, environmentally friendly and easily synthesized, compared to traditional inorganic ferroelectrics. However, how to precisely design a molecular ferroelectric from a non-ferroelectric phase transition molecular system is still a great challenge. Here we designed and constructed a molecular ferroelectric by double regulation of the anion and cation in a simple crown ether clathrate, 4, [K(18-crown-6)]+ [PF6 ]- . By replacing K+ and PF6 - with H3 O+ and [FeCl4 ]- respectively, we obtained a new molecular ferroelectric [H3 O(18-crown-6)]+ [FeCl4 ]- , 1. Compound 1 undergoes a para-ferroelectric phase transition near 350 K with symmetry change from P21/n to the Pmc21 space group. X-ray single-crystal diffraction analysis suggests that the phase transition was mainly triggered by the displacement motion of H3 O+ and [FeCl4 ]- ions and twist motion of 18-crown-6 molecule. Strikingly, compound 1 shows high a Curie temperature (350 K), ultra-strong second harmonic generation signals (nearly 8 times of KDP), remarkable dielectric switching effect and large spontaneous polarization. We believe that this research will pave the way to design and build high-quality molecular ferroelectrics as well as their application in smart materials.

High-Temperature Reversible Phase-Transition Behavior, Switchable Dielectric and Second Harmonic Generation Response of Two Homochiral Crown Ether Clathrates.

Crowning achievement: Two homochiral crown ether clathrates were synthesized which undergo high-temperature reversible phase transition. In addition, second harmonic generation (SHG) responses and abnormal dielectric property further confirm the reversible phase transitions and symmetry breaking behaviors of the structures.

[Effect of acylation stimulating protein on the perilipin and adipophilin expression during 3T3-L1 preadipocyte differentiation.].

Perilipin and adipophilin, two significant lipid droplet (LD)-specific proteins, participate in storing fat or ectopic lipid deposition and fat mobilization in many types of mammalian cells. Acylation stimulating protein (ASP) is a novel adipocyte-derived hormone known for a major determinant for triglyceride synthesis (TGS) and lipid metabolism. The present study was aimed to investigate: (1) whether ASP, rather than insulin, is a powerful potentiator which could physiologically and directly influence TGS during 3T3-L1 preadipocyte differentiation; (2) whether ASP exposure at indicated time points during 3T3-L1 preadipocyte differentiation could influence the gene/protein expression of adipophilin and perilipin. 3T3-L1 preadipocytes were differentiated by traditional hormone cocktail and divided into control, ASP and insulin groups according to the treatment of ASP (1 mmol/L) or insulin (100 nmol/L). ASP-stimulated and insulin-stimulated TGS rate at indicated time points (0 d, 3 d, 6 d, 9 d) were assayed by measuring the incorporation of [(3)H]-oleic acid into TG, and the corresponding glucose transport was assayed by [(3)H]-2-DG uptake. The effects of ASP or insulin on gene/protein expression of adipophilin and perilipin at indicated time points were evaluated by semi-quantitative reverse transcription-polymerase chain reaction (RT-PCR) and Western blot. The results obtained were as follows: (1) on the 3rd and 6th day of differentiation, ASP dramatically enhanced TGS rate compared with control group (P<0.05, P<0.01); There was no significant difference in TGS rate between insulin group and control group; (2) on the 6th and 9th day of differentiation, both ASP and insulin promoted glucose uptake (P<0.05, P<0.01), and the promoting effect in ASP group was greater than that in insulin group; (3) ASP elevated adipophilin gene and protein expression at the very early stage of differentiation (P<0.05, P<0.001) and had no significant effect from the 4th day of differentiation. Perilipin gene and protein expression increased throughout preadipocyte differentiation and its expression was up-regulated following ASP stimulation from the 3rd day of differentiation (P<0.05, P<0.001) to the end of differentiation (P<0.05); (4) Insulin did not affect gene and protein variation pattern of adipophilin and perilipin. Taken together, this study provides evidence that ASP-evoked changes in gene and protein expression of adipophilin and perilipin correlate with ASP-stimulated TGS acceleration, and adipophilin and perilipin are involved in the molecular mechanism of ASP-induced adipogenesis and LD formation.

Density functional theory study of piperidine and diazocine compounds.

Density functional theory calculations at the B3LYP/6-311G** level were performed to predict the heats of formation (HOFs) for three eight-membered ring compounds and four six-membered ring compounds via designed isodesmic reactions. In the isodesmic reactions designed for the computation of HOFs (CH(3)CH(2))(2)NNO(2) and piperidine were chosen as reference compounds. The HOFs for -NO(2) substituted derivations are larger than those of -NF(2) substituent groups. Thermal stability were evaluated via bond dissociation energies (BDE) at the UB3LYP/6-311G** level. As a whole, the homolysis of CNF(2) or CNO(2) bonds is the main step for bond dissociation of the title compounds. Detonation properties of seven title compounds were evaluated by using the Kamlet-Jacobs equation based on the calculated densities and HOFs. It is found that 3,3,7,7-tetrakis(difluoroamino)octahydro-1,5-dinitro-1,5-diazocine (HNFX) and 3,3,5,5-tetrakis (difluoroamino)-1-nitro piperidine (N-nitro TDFAPP), with predicted density of ca. 2.0 g/cm(3), detonation velocity (D) about 9.9 km/s, and detonation pressure (P) of 47GPa that are lager than those of HMX, are expected to be the novel candidates of high energy density materials (HEDMs). The detonation data of 1,3,3,5,7,7-hexanitro-1,5-diazacyclooctane (HNDZ) and TNBDFAPP show that they meet the requirements for HEDMs.

Theoretical studies on four-membered ring compounds with NF2, ONO2, N3, and NO2 groups.

Density functional theory (DFT) method has been employed to study the geometric and electronic structures of a series of four-membered ring compounds at the B3LYP/6-311G** and the B3P86/6-311G** levels. In the isodesmic reactions designed for the computation of heats of formation (HOFs), 3,3-dimethyl-oxetane, azetidine, and cyclobutane were chosen as reference compounds. The HOFs for N(3) substituted derivations are larger than those of oxetane compounds with --ONO2 and/or --NF2 substituent groups. The HOFs for oxetane with --ONO2 and/or --NF2 substituent groups are negative, while the HOFs for N3 substituted derivations are positive. For azetidine compounds, the substituent groups within the azetidine ring affect the HOFs, which increase as the difluoroamino group being replaced by the nitro group. The magnitudes of intramolecular group interactions were predicted through the disproportionation energies. The strain energy (SE) for the title compounds has been calculated using homodesmotic reactions. For azetidine compounds, the NF2 group connecting N atom in the ring decrease the SE of title compounds. Thermal stability were evaluated via bond dissociation energies (BDE) at the UB3LYP/6-311G** level. For the oxetane compounds, the O--NO2 bond is easier to break than that of the ring C--C bond. For the azetidine and cyclobutane compounds, the homolyses of C--NX2 and/or N--NX2 (X = O, F) bonds are primary step for bond dissociation. Detonation properties of the title compounds were evaluated by using the Kamlet-Jacobs equation based on the calculated densities and HOFs. It is found that 1,1-dinitro-3,3-bis(difluoroamino)-cyclobutane, with predicted density of ca. 1.9 g/cm(3), detonation velocity (D) over 9 km/s, and detonation pressure (P) of 41 GPa that are lager than those of TNAZ, is expected to be a novel candidate of high energy density materials (HEDMs). The detonation data of nitro-BDFAA and TNCB are also close to the requirements for HEDMs.

Strain energies of cubane derivatives with different substituent groups.

Homodesmotic reaction and isodesmotic reaction were designed for the computation of strain energies (SE) for a series of cubane derivatives. Total energies of the optimized geometric structures at the DFT-B3LYP/6-31G* level were used to derive the SE. The SE value of cubane is 169.13 kcal/mol for homodesmotic reaction, which is in good agreement with the experimental value. The variation of SE with respect to the number of substituents is similar for the homodesmotic reaction and isodesmotic reaction. The SE values of polynitrocubane and polydifluoroaminocubane increase slightly as up to four substituent groups being added to the cage skeleton. On contrary, the SE dramatically increases when the number of substituent groups m increases from 5 up to 8. For polynitratocubane, the SE decreases slightly at the beginning then increases as the number of group increases. For polyazidocubane, there are very small group effects on the SE. Among four types of substituent groups, the nitro group has greatest effect on the strain energy of caged cubane skeleton. The calculated SE value of octanitrocubane is 257.20 kcal/mol, while that of octaazidocubane is 166.48 kcal/mol via isodesmotic reaction. The azido group releases the strain energy of cubane skeleton when the number of azido groups is less than 7. The interactions among the substituted groups deviated from group additivity. The substituted groups withdraw electrons from the cubane, reducing the repulsion between C-C bonds and resulting the release the strain of the skeleton for isomers with fewer substituents. Group repulsions increase sharply with more and more nitro, nitrato and difluoroamino groups being attached to cubane, resulting large strains of the skeleton. The average negative charges of the substituted groups influence the strain energy of cubane derivatives.