Effects of Bright Light Therapy on Agitation Among Older Adults Living with Dementia in Macao: A Pilot Study.

A randomized controlled trial was conducted to examine the effects of bright light therapy on agitation in older adults with dementia in Macao. This study involved 31 participants: 10 in the outdoor light treatment group, 11 in the indoor light-box treatment group, and 10 in the control group. Significant reductions in agitation were observed in the two treatment groups over four weeks compared to the control group. However, no statistical difference in cognitive function between experimental and control groups was found. This study supports the use of bright light therapy to reduce agitation in older people with dementia.

Shape-Persistent Dendrimers.

Dendrimers have a diverse and versatile morphology, frequently consisting of core, linking, and peripheral moieties. Dendrimers with flexible linkers, such as PAMAM, cannot retain the persistent shape of molecules, and this has been widely explored and reviewed previously; nevertheless, dendrimers with stiff linkers can preserve the persistent shape of the dendrimers, which has been reported considerably less. This review thus focuses on addressing shape-persistent dendrimers with rigid linking moieties discovered in recent years, i.e., from 2012 to 2023. Shape-persistent dendrimers with an interstitial gap between the dendritic frames in the solid state may or may not let the intramolecular void space be accessible for guest molecules, which largely depends on whether their peripheral groups are flexible or non-flexible. In this paper, eight articles on shape-persistent dendrimers with a flexible alkyl periphery, which may exhibit mesogenic phases upon thermal treatment, and eight articles on shape-persistent dendrimers with a non-flexible periphery, which may allow external ions, gases, or volatile organic compounds to access the interstitial gaps between dendritic frames, are reviewed.

Dendrimers with Tetraphenylmethane Moiety as a Central Core: Synthesis, a Pore Study and the Adsorption of Volatile Organic Compounds.

Reasonable yields of two dendrimers with central tetraphenylmethane and peripheral 3,5-di-(tert-butanoylamino)benzoylpiperazine moieties are prepared. These dendrimers have a void space in the solid state so they adsorb guest molecules. Their BET values vary, depending on the H-bond interaction between the peripheral moiety and the gas molecules, and the dendritic framework that fabricates the void space is flexible. In the presence of polar gas molecules such as CO2, the BET increases significantly and is about 4-8 times the BET under N2. One dendrimer adsorbs cyanobenzene to a level of 436 mg/g, which, to the authors' best knowledge, is almost equivalent to the highest reported value in the literature.

Adsorbing Volatile Organic Chemicals by Soluble Triazine-Based Dendrimers under Ambient Conditions with the Adsorption Capacity of Pyridine up to 946.2 mg/g.

Two triazine-based dendrimers with peripheral 1,3,5-triamidobenzene (1-3-5-TAB) functionality were prepared, and their void spaces in the bulk solid were investigated. We examined dendrimers of three core lengths and determined the one with the longest core exhibits the largest void space because the peripheral amides were not imbedded in the internal space of each dendritic molecule. The new dendrimers as solids were observed to adsorb volatile organic chemicals efficiently. Importantly, because the dendrimers are soluble in organic solvents, the adsorbed VOCs can be quantified by 1H-NMR spectroscopy by choosing a chemical shift (δ) of dendrimers as the internal standard to exclude interfering impurity signals, a much simpler and more efficient protocol than the traditional GC technique for the VOC quantification. One dendrimer was found to adsorb 24 equivalents of pyridine, so its adsorption capacity is equivalent to 946.2 mg/g. This is a more than 2-fold increase than the reported values by other porous materials.

BTLA-expressing CD11c antigen presenting cells in patients with active tuberculosis exhibit low capacity to stimulate T cell proliferation.

Despite past extensive studies on B and T lymphocyte attenuator (BTLA)-mediated negative regulation of T cell activation, the role of BTLA in antigen presenting cells (APCs) in patients with active pulmonary tuberculosis (ATB) remains poorly understood. Here, we demonstrate that BTLA expression on CD11c APCs increased in patients with ATB. Particularly, BTLA expression in CD11c APCs was likely associated with the attenuated stimulatory capacity on T cells (especially CD8+ T cell) proliferation. BTLA-expressing CD11c APCs showed lower antigen uptake capacity, lower CD86 expression, higher HLA-DR expression, and enhanced IL-6 secretion, compared to counterpart BTLA negative CD11c APCs in healthy controls (HC). Interestingly, BTLA-expressing CD11c APCs from ATB patients displayed lower expression of HLA-DR and less IL-6 secretion, but higher expression of CD86 than those from HC volunteers. Mixed lymphocyte reaction suggests that BTLA expression is likely associated with positive rather than conventional negative regulation of CD11c APCs stimulatory capacity. This role is impaired in ATB patients manifested by low expression of HLA-DR and low production of IL-6. This previous unappreciated role for BTLA may have implications in the prevention and treatment of patients with ATB.

Anion-Directed Copper(II) Metallocages, Coordination Chain, and Complex Double Salt: Structures, Magnetic Properties, EPR Spectra, and Density Functional Study.

A series of Cu(II) metallo-assemblies showing anion-directed structural variations, including five metallocages [(G(n-) )⊂{Cu2 (Hdpma)4 }]((8-n)+) (A(-) )8-n (G(n-) =NO3 (-) , ClO4 (-) , SiF6 (2-) , BF4 (-) , SO4 (2-) ; A(-) =NO3 (-) , ClO4 (-) , BF4 (-) , CH3 SO4 (-) ; Hdpma=bis(3-pyridylmethyl)ammonium cation), a complex double salt, namely, (H3 dpma)4 (CuCl4 )5 Cl2 , and a coordination chain, namely, [Cu2 (dpma)(OAc)4 ], are reported. The influence of the anion can be explained by its coordinating ability, the affinity of which for the Cu(II) center interferes significantly with metallocage formation, and its shape, which offers host-guest recognition ability to engage in weak metal-anion coordination and hydrogen bonding to the organic ligand, which are responsible for metallocage templation. EPR studies of these metallocages in the powder phase at room temperature and 77 K showed a trend of the g values (g|| >2.10>g⊥ >2.00) indicating a dx2-y2 -based ground state with square-pyramidal geometry for the Cu(II) centers. The magnetism of these metallocages can be interpreted as the result of a combination of relatively small magnetic coupling integrals and a substantial contribution of temperature-independent paramagnetism (TIP). The weak magnetic interaction is corroborated by the results of DFT calculations and the EPR spectra. Availability of the low-lying state for spin population was confirmed by a magnetization study, which revealed a magnetic moment approaching 2Nß, which would explain the presence of the larger TIP term.

Converting Nonliquid Crystals into Liquid Crystals by N-Methylation in the Central Linker of Triazine-Based Dendrimers.

Two triazine-based dendrimers were successfully prepared in 60-75% yields. These newly prepared dendrimers 2a and 2b containing the -NMe(CH2)2NMe- and the -NMe(CH2)4NMe- linkers between two G3 dendrons, respectively, exhibit columnar phases during the thermal process. However, the corresponding dendrimers 1a and 1b containing the -NH(CH2)2NH- and the -NH(CH2)4NH- linkers between two G3 dendrons, respectively, do not show any LC phases on thermal treatment. Computational investigations on molecular conformations reveal that N-methylation of the dendritic central linker leads dendrimers to possess more isomeric conformations and thus successfully converts non-LC dendrimers (1a and 1b) into LC dendrimers (2a and 2b).

An Unconventional Approach to Induce Liquid-Crystalline Phases of Triazine-Based Dendrons by Breaking Their Self-Assembly into Dimers.

Three triazine-based dendrons (1 a-c) were successfully prepared in 70-83 % yields. These newly prepared dendrons are found to be liquid crystalline (LC). Computational investigations on molecular conformations and dipoles of triazine-based dendrons reveal that the substituent on the central triazine unit interrupts strong dipole or H-bond interactions to avoid dimeric formation. The obtained dendrons, not favouring self-assembly into dimers but showing LC behaviours, provides evidence for an approach contrary to the conventional method of inducing LC behaviours of dendrons by dimer or trimer formation, mostly through H-bond interactions.

A small change in central linker has a profound effect in inducing columnar phases of triazine-based unconventional dendrimers.

Four unconventional triazine-based dendrimers have been prepared and characterized by (1) H and (13) C NMR spectroscopies, mass spectrometry, and elemental analysis. Based on DSC studies, polarizing microscopy, and powder XRD, two of these dendrimers, containing linkers with an odd number of carbon atoms, were observed to display columnar liquid-crystalline phases during thermal treatment. However, the other two dendritic analogues, containing linkers with an even number of carbon atoms, were not observed to behave correspondingly. Based on computer simulation, we reasonably assume that the dendrimers with an odd number of carbon atoms in their linkers distort their molecular shape and adopt two isomeric structures due to asymmetrical congestion. This reduces the molecular π-π face-to-face interaction, which in turn causes the dendrimers to form columnar LC phases during thermal treatment. However, the dendrimers with an even number of carbon atoms in their linkers have more symmetrical skeletons and do not display any liquid-crystalline phase upon thermal treatment. This new strategy should be applicable for eliciting the columnar liquid-crystalline properties of other types of unconventional dendrimers with rigid frameworks.

Determination of optimal mining width for coal mining under the slope by of using numerical simulation.

The stability of slope is critical important topic in rock mass engineering. In Panzhihua #7 Coal Mine, the coal mining is occurred under the slope, to obtain the optimal mining width, 125 numerical simulations were conducted, and the corresponding FOS was calculated. From the analysis of the numerical simulation results, it can be found that FOS decrease and then increase with increasing of filling length, meanwhile, the FOS is minimum value when the filling length is within the ranges of 10 m and 20 m, which is under the toe of slope. Furthermore, the minimum FOS decrease with increasing of mining width. Considered the stability of the slope and mining economy, the mining width is set to 6m, and the numerical simulation results is applied to the engineering practice. To guarantee the safety of the slope, some monitoring points were distributed on the slope, the displacement from numerical simulation and engineering practice is quite close, indicating the numerical simulation results is reliable, and the mining width is reasonable.

Administering immunotherapy after anti-vascular targeted therapy improves overall survival of patients with metastatic clear cell renal cell carcinoma.

BACKGROUND: The Food and Drug Administration of the United States has approved several drugs for treating advanced metastatic renal cell carcinoma, including anti-vascular tyrosine kinase inhibitors (TKIs) and immune checkpoint inhibitors (ICIs). Options for first-line therapy include monotherapy or combination therapy. However, selecting a suitable first-line and second-line treatments to improve overall survival remains an unresolved issue. OBJECTIVE: To evaluate the overall survival (OS) and progression-free survival (PFS) of patients with metastatic clear cell renal cell carcinoma (mRCC). Patients were divided into several grouped according to the treatment sequence of TKI and anti PD-1 administration. The overall survival benefit was evaluated based on the order of administration of anti PD-1 and TKI. PATIENTS AND METHODS: In this retrospective propensity-matched cohort study, we identified 135 patients with mRCC treated at the Affiliated Cancer Hospital of Shandong First Medical University from January 1, 2017, to December 31, 2022. These patients had received anti PD-1 treatment as part of their first or second line of therapy. Statistical analysis was performed from June 1, 2023, to August 1, 2023. The primary outcome measure was OS, from the date of diagnosis to death or the last follow-up. PFS was monitored during treatment. Survival analyses were conducted using Cox proportional hazards regression and Kaplan-Meier estimates. By comparing the complete treatment course of patients, the survival of patients in different groups was compared according to the number of immunotherapy lines. RESULTS: The final cohort comprised 135 patients, of whom 84 received first-line therapy with anti PD-1 (include 6 patients treated with anti PD-1 (tislelizumab, carrelizumab, toripalimab or sintilizumab) alone and 78 patients treated with anti PD-1 combined with anti-vascular TKI (axitinib, sunitinib, solfanitinib or pazopanib)). The remaining 51 patients were treated with anti PD-1 as second-line therapy following an initial regime of TKIs. Patients were initially categorized based on whether anti PD-1 were used in the first-line treatment. It was observed that the OS of patients receiving first-line targeted therapy was higher than those receiving first-line immunotherapy, with a median OS of 33 months versus 15 months. To investigate this outcome further, we refined the patient groups based on the administration sequence of anti PD-1 and TKIs in the treatment regimen. We found that the median PFS of patients with first-line treatments of TKI combined with anti PD-1 was 3.5 months, compared to 14.5 months when TKI combined with anti PD-1 followed first-line TKI (p=0.0092). The median PFS for second-line treatments was 6.5 months versus 15 months (p=0.0014). Similarly, the median OS was 16.66 months and 31.88 months, respectively (p=0.008). CONCLUSIONS: This study indicates that administering immunotherapy following anti-vascular therapy significantly enhances both OS and PFS compared to other sequences of therapies. This finding provides valuable insights and robust data support for clinical decision-making regarding treatment sequencing.

Response of anammox to organics with different degradation characteristics and exposure time: Performance, sludge characteristics and bacterial community.

The effects of typical organic compounds including easily degradable organic matters sodium acetate, yeast and methanol, and refractory organic matter (ROM) humic acid on anaerobic ammonium oxidation (anammox) systems in short-term and medium-term exposure time were studied. During short-term experiments, nitrogen removal activity (NRA) was inhibited at sodium acetate level of 150 mg L-1 total organic carbon (TOC) and methanol level of 30-150 mg L-1 TOC, but humic acid and yeast (≤150 mg L-1 TOC) enhanced nitrogen removal in anammox systems. The greatest NRA of 30.10 mg TN g-1 VSS h-1 was recorded at yeast level of 90 mg L-1 TOC. In medium-term experiments, organics significantly inhibited the nitrogen removal ability. As a ROM, humic acid enhanced sludge aggregation and biological diversity, but decreased the bioactivity and extracellular polymeric substances levels. Due to the endogenous denitrification, the relative abundance of anammox bacteria (AnAOB) was decreased. Candidatus Kuenenia is still dominant in sludge with methanol and humid acid, but AnAOB are not dominant due to the addition of sodium acetate and yeast. This research would be beneficial for the full-scale application of the anammox process in treating real wastewater with organics and ammonia.

Preparation of unconventional dendrimers that contain rigid NH-triazine linkages and peripheral tert-butyl moieties for CO2 -selective adsorption.

Three unconventional dendrimers that contained rigid NH-triazine linkages and peripheral tert-butyl moieties were prepared by using a convergent approach and characterized by (1)H and (13)C NMR spectroscopy, mass spectrometry, and elemental analysis. Based on a thermogravimetric analysis study, these dendrimers were observed to display thermal stability at about 300 °C. The NH-triazine moiety, which possessed protonated and proton-free nitrogen sites (like the imidazole unit), displayed the capture of polarizable CO2 molecules through hydrogen-bond and/or dipole-quadrupole interactions. In addition, the adsorption of various amounts of CO2 and N2 at different pressures suggests that the dendritic pores, which arise from the stacking of the middle co-planar and rim protuberant dendrimers, Gn -N∼N-Gn (n=1-3), either swell or shrink at high pressure, thus indicating that these dendrimers may have a breathing ability.

Synthesis and antitumor activity of tetrandrine derivatives.

Tetrandrine possesses antitumor activity, however, only a few studies on its structure modification were reported. To improve the antitumor activity of tetrandrine, 20 new tetrandrine derivatives were designed and synthesized by Sonogashira and Suzuki reactions. Their antitumor activities were evaluated against three tumor cell lines including A549, HepG2, and BGC-823 by methyl thiazolyl tetrazolium assay with taxol as a positive control. The results showed that compounds 2c and 2g were highly potent against BGC-823 cell line, and compounds 1i and 1k showed particular activity against HepG2 cells. These results demonstrated that compounds 1i, 1k, 2c, and 2g were promising leads for further investigation.

Induction of the columnar phase of unconventional dendrimers by breaking the C2 symmetry of molecules.

Two triazine-based unconventional dendrimers were prepared and characterized by (1)H and (13)C NMR spectroscopy, mass spectrometry, and elemental analysis. Differential scanning calorimetry, polarizing microscopy, and powder XRD studies showed that these dendrimers display columnar liquid-crystalline phases during thermal treatment. This is ascribable to breaking of their C(2) symmetry. The molecular conformations of prepared dendrimers were obtained by computer simulation with the MM3 model of the CaChe program in the gas phase. The simulation showed that the conformations of the prepared dendrimers are rather flat and disfavor formation of the LC phase. However, due to C(2)-symmetry breaking, the prepared dendrimers have structural isomers in the solid state and thus show the desired columnar phases. This new strategy should be applicable to other types of unconventional dendrimers with rigid frameworks.

Multielectron redox chemistry of a neutral, NIR-active, indigo-pillared Re(I)-based triangular metalloprism.

Self-assembled, hexarhenium(I), triangular metalloprism compound [{(CO)(3)Re(µ-2)Re(CO)(3)}(3)(µ(3)-1)(2)] (3) featuring three bis-chelating pillarlike indigo dianions (µ-2), each of which connects two fac-Re(CO)(3) cores, which are interconnected by a tritopic N donor, that is, a 2,4,6-tris(4-pyridyl)-1,3,5-triazine (µ(3)-1, tPyTz) ligand, has been synthesized in high yield and characterized. Metalloprism 3 exhibits a strong absorption in the near-infrared (NIR) region. The reversible, multielectron redox properties of the electrogenerated 3(n) species, where n=3+, 0, 3-, 4-, 5-, 8-, in the visible and especially in the NIR region were investigated in THF solution by cyclic voltammetry (CV), chronocoulometry, EPR spectroscopy, and thin-layer UV/Vis/NIR spectroelectrochemistry (SEC). Stepwise, site-specific electrochemical reductions lead to the formation of a series of highly stable ion (radical) species in which electrons associated with µ-2 or µ(3)-1 components of the molecule can be clearly distinguished. An EPR investigation revealed interaction of unpaired electrons with the metal nuclei ((185,187)Re, I=5/2) in the reduced intermediates. The framework has C(2) symmetry, and accidental degeneracies suffice. Detailed theoretical calculations by structure-based DFT confirm that the triply degenerate HOMO has ≥70% indigo character with a sizable dπ-Re character, while the LUMO is dominated by the triply degenerate indigo ligands, and the LUMO+1 by doubly degenerate tPyTz ligands. A comparison of 3 and previously reported 2,2'-bis-benzimidazolate- (BiBzlm) or alkoxy-pillared Re(I) metalloprisms indicates a very low switching potential with a potential window of less than 1 V and reversibly accessible optical properties with higher stability of the intermediates. The properties exhibited by 3 appear to be due to the slight tuning of the bridging ligand from N,N(-) to N,O(-).

Formation of columnar liquid crystals on the basis of unconventional triazine-based dendrimers by the C3-symmetric approach.

Two series of unconventional triazine-based dendrimers with C(2) symmetry and C(3) symmetry were prepared. The newly prepared C(3)-symmetrical dendrimers were characterized by (1)H and (13)C NMR spectroscopy, mass spectrometry, and elemental analysis. Differential scanning calorimetry, polarizing microscopy, and powder XRD showed that the C(3)-symmetrical dendrimers display columnar liquid-crystalline phases during thermal treatment, but the C(2)-symmetrical dendrimers were not observed to behave correspondingly. The molecular conformations of C(3)- and C(2)-symmetrical dendrimers were obtained by computer simulation with the MM2 model of the CaChe program in the gas phase. The simulation results reasonably explain the different mesogenicities of C(3)- and C(2)-symmetric dendrimers. This new strategy should be applicable to other types of unconventional dendrimers with rigid frameworks for displaying columnar liquid-crystalline behavior.

Infinite copper(II) coordination architectures from a resonative aminotriazine-derived tripodal ligand: synthesis, structures, and magnetic properties.

The ligand 2,4,6-tris(2-picolylamino)-1,3,5-triazine (o-H3tpat) with essentially resonative structure and two copper(II)-based one-dimensional coordination chain structures, [Cu3Cl5(o-H2tpat)(H2O)]·MeOH·CH2Cl2 (1) and [Cu2(o-H2tpat)(H2O)(MeOH)(NO3)2](NO3)·3MeOH (2), with different structural patterns have been synthesized and characterized using single crystal X-ray diffraction analysis. For o-H3tpat, two crystalline forms showing different solid-state structural features are obtained from MeOH/Et2O (form I) and CH2Cl2/Et2O (form II), respectively. The o-H3tpat form I adopts an asymmetric-configured all-amino resonative tautomer with three cis-trans-trans-arranged pyridyl groups, whereas the o-H3tpat form II adopts also an identical resonative structure but where two of the three pyridyl groups are in a cis-manner and the third one is nearly coplanar with the central aminotriazine core. On the other hand, the designed tripodal ligand in both Cu(II)-complexes serves as a monoanion, o-H2tpat(-), which suits a propeller-configured all-imino resonative structure in 1 and a syn-anti-configured amino-imino-imino resonative structure in 2. These observations significantly indicate that the o-H3tpat ligand can self-adjust and interconvert its conformation via a possible structure transformation associated with proton-shift to adapt a change in the crystallization and self-assembly reaction systems. In the magnetic point of view, 1 is treated as repeated chains composed of infinite {Cu6Cl10} units wherein the hexanuclear unit is further decomposed to one {Cu(II)4Cl6} and two magnetically isolated {Cu(II)Cl2} subunits. Antiferromagnetic interactions are found for the Cu4 subunits (g = 2.33, 2J1 = -5.6 cm(-1), 2J2 = -8.6 cm(-1), 2J3 = -4.1 cm(-1), and J4 held to zero). For 2, it is considered as an infinite chain that composes of Cu2 units antiferromagnetically coupled (g = 2.03, 2J1 = -0.2 cm(-1)). The small antiferromagnetic exchange constants in both 1 and 2 suggest that the unpaired spins do not effectively interact through the tripodal o-H2tpat(-) ligands.

Strategies to improve electrocatalytic performance of MoS2-based catalysts for hydrogen evolution reactions.

Electrocatalytic hydrogen evolution reactions (HERs) are a key process for hydrogen production for clean energy applications. HERs have unique advantages in terms of energy efficiency and product separation compared to other methods. Molybdenum disulfide (MoS2) has attracted extensive attention as a potential HER catalyst because of its high electrocatalytic activity. However, the HER performance of MoS2 needs to be improved to make it competitive with conventional Pt-based catalysts. Herein, we summarize three typical strategies for promoting the HER performance, i.e., defect engineering, heterostructure formation, and heteroatom doping. We also summarize the computational density functional theory (DFT) methods used to obtain insight that can guide the construction of MoS2-based materials. Additionally, the challenges and prospects of MoS2-based catalysts for the HER have also been discussed.

Converting non-Mesogenic to Mesogenic Stacking of Amino-s-Triazine-Based Dendrons with p-CN Phenyl Unit by Eliminating Peripheral Dipole.

Three new amino-s-triazine-based dendrons, 1a, 1b, and 1c, containing an aryl-CN moiety in the dendritic skeleton were prepared in 72-81% yields (1a: R1 = - N(n-C8H17)2, R2 = n-OC8H17, 1b: R1 = R2 = - N(n-C8H17)2, 1c: R1 = - N(n-C8H17)2, R2 = - N(n-C4H9)2). Dendrons 1a with N(n-C8H17)2 and n-OC8H17 peripheral substituents, surprisingly, did not show any mesogenic phase during the thermal process. However, non-mesogenic 1a can be converted to mesogenic 1b or 1c by eliminating the peripheral dipole arising from the alkoxy substituent; dendron 1b only comprising the same N(n-C8H17)2 peripheral groups showed a ~25 °C mesogenic range on heating and ~108 °C mesogenic range on cooling. In contrast, dendron 1c possessing different N(n-CmH2m+1)2 (m = 8 versus m = 4) peripheral units, having similar stacking as 1b, exhibited a columnar phase on thermal treatment, but its mesogenic range (~9 and ~66 °C on heating and cooling, respectively) was much narrower than that of 1b, attributed to 1c's less flexible alkyl chains in the peripheral part of dendron. Dendron 1a with the alkoxy substituent in the peripheral skeleton, creating additional dipole correspondingly, thus, leads to the dendritic molecules having a non-mesogenic stacking. Without the peripheral dipole for intermolecular side-by-side interaction, dendrons 1b and 1c exhibit a columnar phase on thermal treatment because of the vibration from the peripheral alkyl chain.