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Min-Jie Wang,1– 3 Jiayu Wang,4 Houdi Zhang,2,3 Fang-Bin Hao,1– 3 Gan Gao,1– 3 Si-Meng Liu,1– 3 Xiao-Peng Wang,1– 3 Jing-Jie Li,1– 3 Zheng-Xing Zou,2,3 Qing-Bao Guo,1– 3 He-Guan Fu,2,3 Yi-Qin Han,2,3 Cong Han,2,3 Lian Duan2,3 1Chinese PLA Medical School, Beijing, People’s Republic of China; 2Department of Neurosurgery, the First Medical Centre, Chinese PLA General Hospital, Beijing, People’s Republic of China; 3Department of Neurosurgery, the Fifth Medical Centre, Chinese PLA General Hospital, Beijing, People’s Republic of China; 4Department of Immunology, Institute of Basic Medical Sciences Chinese Academy of Medical Sciences, School of Basic Medicine Peking Union Medical College, Beijing, People’s Republic of ChinaCorrespondence: Lian Duan; Cong Han, Department of Neurosurgery, Department of Neurosurgery, the Fifth Medical Centre (South Campus), Chinese PLA General Hospital, No. 8 Dong-Da Street, Fengtai District, Beijing, 100071, People’s Republic of China, Tel +86-10-66947389 ; +86-13466346163 ; +86-10-66947388, Fax +86-10-62177976, Email duanlian307@sina.com; hc82225@126.comBackground: The immune system plays an important role in the onset and development of moyamoya disease (MMD), but the specific mechanisms remain unclear. This study aimed to explore the relationship between the expression of complements and immunoglobulin in serum and progression of MMD.Methods: A total of 84 patients with MMD and 70 healthy individuals were enrolled. Serum immunoglobulin and complement C3 and C4 expression were compared between healthy individuals and MMD patients. Follow-up was performed at least 6 months post-operation. Univariate and multivariate analysis after adjusting different covariates were performed to explore predictive factors associated with vasculopathy progression. A nomogram basing on the results of multivariate analysis was established to predict vasculopathy progression.Results: Compared to healthy individuals, MMD patients had significantly lower expression of serum complements C3 (P = 0.003*). Among MMD patients, C3 was significantly lower in those with late-stage disease (P = 0.001*). Of 84 patients, 27/84 (32.1%) patients presented with vasculopathy progression within a median follow-up time of 13.0 months. Age (P=0.006*), diastolic blood pressure (P=0.004*) and serum complement C3 expression (P=0.015*) were associated with vasculopathy progression after adjusting different covariables.Conclusion: Complement C3 is downregulated in moyamoya disease and decreases even further in late–Suzuki stage disease. Age, diastolic blood pressure and serum complement C3 expression are associated with vasculopathy progression, suggesting that the complement might be involved in the development of moyamoya disease.Keywords: moyamoya disease, complement, Suzuki stage, nomogram

Objective: Diabetes is often linked to poorer outcomes in patients with moyamoya disease (MMD). However, experience has shown that certain individuals with diabetes have favorable outcomes after encephaloduroarteriosynangiosis (EDAS). The authors aimed to develop a nomogram to predict good neoangiogenesis in patients with MMD and type 2 diabetes mellitus (T2DM) to aid neurosurgeons in the identification of suitable candidates for EDAS., Methods: Adults with MMD and T2DM who underwent EDAS between June 2004 and December 2018 were included in the analysis. In total, 126 patients (213 hemispheres) with MMD and T2DM from the Fifth Medical Centre of the Chinese PLA General Hospital were included and randomly divided into training (152 hemispheres) and internal validation (61 hemispheres) cohorts at a ratio of 7:3. Univariate logistic and least absolute shrinkage and selection operator regression analyses were used to identify the significant factors associated with good neoangiogenesis, which were used to develop a nomogram. The discrimination, calibration, and clinical utility were assessed., Results: A total of 213 hemispheres in 126 patients were reviewed, including 152 (71.36%) hemispheres with good postoperative collateral formation and 61 (28.64%) with poor postoperative collateral formation. The authors selected 4 predictors (FGD5 rs11128722, VEGFA rs9472135, Suzuki stage, and internal carotid artery [ICA] moyamoya vessels) for nomogram development. The C-indices of the nomogram in the training and internal validation cohorts were 0.873 and 0.841, respectively. The nomogram exhibited a sensitivity of 84.5% and specificity of 81.0%. The positive and negative predictive values were 92.1% and 66.7%, respectively. The calibration curves indicated high predictive accuracy, and receiver operating characteristic curve analysis showed the superiority of the nomogram. The decision-making analysis validated the fitness and clinical application value of this nomogram. Then a web-based calculator to facilitate clinical application was generated., Conclusions: The nomogram developed in this study accurately predicted neoangiogenesis in patients with MMD and T2DM after EDAS and may assist neurosurgeons in identifying suitable candidates for indirect revascularization surgery.

Objective: The aim of this study was to develop and validate a predictive nomogram model for long-term rebleeding events in patients with hemorrhagic moyamoya disease (HMMD)., Methods: In total, 554 patients with HMMD from the Fifth Medical Center of the Chinese PLA General Hospital (5-PLAGH cohort) were included and randomly divided into training (390 patients) and internal validation (164 patients) sets. An independent cohort from the First Medical Center and Eighth Medical Center of Chinese PLA General Hospital (the 1-PLAGH and 8-PLAGH cohort) was used for external validation (133 patients). Univariate Cox regression analysis and least absolute shrinkage and selection operator (LASSO) regression algorithm were used to identify significant factors associated with rebleeding, which were used to develop a nomogram for predicting 5- and 10-year rebleeding., Results: Intraventricular hemorrhage was the most common type of cerebral hemorrhage (39.0% of patients in the 5-PLAGH cohort and 42.9% of the 1-PLAGH and 8-PLAGH cohort). During the mean ± SD follow-up period of 10.4 ± 2.9 years, 91 (16.4%) patients had rebleeding events in the 5-PLAGH cohort. The rebleeding rates were 12.3% (68 patients) at 5 years and 14.8% (82 patients) at 10 years. Rebleeding events were observed in 72 patients (14.3%) in the encephaloduroarteriosynangiosis (EDAS) surgery group, whereas 19 patients (37.3%) experienced rebleeding events in the conservative treatment group. This difference was statistically significant (p < 0.001). We selected 4 predictors (age at onset, number of episodes of bleeding, posterior circulation involvement, and EDAS surgery) for nomogram development. The concordance index (C-index) values of the nomograms of the training cohort, internal validation cohort, and the external validation cohort were 0.767 (95% CI 0.704-0.830), 0.814 (95% CI 0.694-0.934), and 0.718 (95% CI 0.661-0.775), respectively. The nomogram at 5 years exhibited a sensitivity of 48.1% and specificity of 87.5%. The positive and negative predictive values were 38.2% and 91.3%, respectively. The nomogram at 10 years exhibited a sensitivity of 47.1% and specificity of 89.1%. The positive and negative predictive values were 48.5% and 88.5%, respectively., Conclusions: EDAS may prevent rebleeding events and improve long-term clinical outcomes in patients with HMMD. The nomogram accurately predicted rebleeding events and assisted clinicians in identifying high-risk patients and devising individual treatments. Simultaneously, comprehensive and ongoing monitoring should be implemented for specific patients with HMMD throughout their entire lifespan.

Background: The relationship between anterior cerebral artery (ACA) occlusion and moyamoya disease (MMD) has rarely been studied. In this study, we focused on a special type of MMD: isolated ACA-occlusive MMD. We investigated clinical attributes, genotypes and progression risk factors in patients with ACA-occlusive MMD, providing initial insights into the relationship between ACA occlusion and MMD., Methods: We retrospectively analysed digital subtraction angiography (DSA) from 2486 patients and diagnosed 139 patients with ACA-occlusive MMD. RNF213 p.R4810K (rs112735431) mutation analysis was performed. Patients were categorised into progression and non-progression groups based on whether they progressed to typical MMD. Differences in clinical characteristics, neuropsychological assessment, radiological findings and genotypes were evaluated. Logistic regression analyses identified risk factors for ACA-occlusive MMD progression., Results: The median age of patients with ACA-occlusive MMD was 36 years, and the primary symptom was transient ischaemic attack (TIA). 72.3% of ACA-occlusive MMD patients had cognitive decline. Of 116 patients who underwent RNF213 gene mutation analysis, 90 patients (77.6%) carried the RNF213 p.R4810K GG allele and 26 (22.4%) carried the GA allele. Of 102 patients with follow-up DSA data, 40 patients (39.2%) progressed. Kaplan-Meier curve estimates indicated a higher incidence of ischaemic stroke in the progression group during follow-up (p=0.035). Younger age (p=0.041), RNF213 p.R4810K GA genotype (p=0.037) and poor collateral compensation from the middle cerebral artery (MCA) to ACA (p<0.001) were risk factors of ACA-occlusive MMD progression to typical MMD., Conclusions: Cognitive decline and TIA might be the main manifestations of ACA-occlusive MMD. Isolated ACA occlusion may be an early signal of MMD. The initial lesion site of MMD is not strictly confined to the terminal portion of the internal carotid artery. Younger patients, patients with RNF213 p.R4810K GA genotype or those with inadequate MCA-to-ACA compensation are more likely to develop typical MMD., Competing Interests: Competing interests: None declared., (© Author(s) (or their employer(s)) 2024. Re-use permitted under CC BY-NC. No commercial re-use. See rights and permissions. Published by BMJ.)

Objective: This study aimed to explore the long-term outcome of unilateral moyamoya disease and predict the clinical and genetic factors associated with contralateral progression in unilateral moyamoya disease., Methods: We retrospectively recruited unilateral moyamoya disease patients with available genetic data who underwent encephaloduroarteriosynangiosis (EDAS) surgery at our institution from January 2009 to November 2017. Long-term follow-up data, including clinical outcomes, angiographic features, and genetic information, were analyzed., Results: A total of 83 unilateral moyamoya disease patients with available genetic data were enrolled in our study. The mean duration of clinical follow-up was 7.9 ± 2.0 years. Among all patients, 19 patients demonstrated contralateral progression to bilateral disease. Heterozygous Ring Finger Protein 213 p.R4810K mutations occurred significantly more frequently in unilateral moyamoya disease patients with contralateral progression. Furthermore, patients with contralateral progression typically demonstrated an earlier age of onset than those with non-progressing unilateral moyamoya disease. In the contralateral progression group, posterior circulation involvement was observed in 11 (11/19, 57.9%) patients compared to 12 (12/64, 18.8%) in the non-contralateral progression group ( P  = 0.001). The time to peak of cerebral perfusion and neurological status showed significant postoperative improvement., Conclusion: Long-term follow-up revealed that the EDAS procedure might provide benefits for unilateral moyamoya disease patients. Ring Finger Protein 213 p.R4810K mutations, younger age, and posterior circulation involvement might predict the contralateral progression of unilateral moyamoya disease., Competing Interests: The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:Lian Duan reports article publishing charges was provided by National Natural Science Foundation of China. Qian-Nan Wang reports article publishing charges was provided by National Natural Science Foundation of China. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2024 The Authors.)

Supramolecular luminescent material with switchable behavior and photo-induced aggregation with emission enhancement is a current research hot spot. Herein, a size-tunable nano-supramolecular assembly with reversible photoluminescent behavior was constructed by noncovalent polymerization of diarylethene-bridged bis(coumarin) derivative (DAE-CO), cucurbit[7]uril (CB[7]), and β-cyclodextrin-grafted hyaluronic acid (HACD). Benefiting from the macrocyclic confinement effect, the guest molecule DAE-CO was included into the cavity of CB[7] to give enhanced fluorescence emission of the resulting DAE-CO⊂CB[7] 2 with longer lifetime at 432 nm to 1.43 ns, thereby further enhancing fluorescence output and lifetime (1.46 ns) when further assembled with HACD, compared with the free DAE-CO (0.95 ns). In addition, DAE-CO, DAE-CO⊂CB[7] 2 , and DAE-CO⊂CB[7] 2 &HACD all possessed characteristics of aggregation-induced emission and reversible photo-switched structural interconversion, exhibiting an obvious photophysical activation phenomenon of self-aggregation into larger nanoparticles with increase in fluorescence emission intensity, lifetime, and size after irradiation, which could be increased step by step with the alternating irradiation of 254 nm (5 min) or >600 nm (30 s) repeated 7 times. These supramolecular assemblies were successfully used in the tumor cells' targeted imaging and anti-counterfeiting because of the capability of HACD for recognizing specific receptors overexpressed on the surface of tumor cells and the excellent photo-regulated switch ability of DAE-CO, providing an approach of constructing photo-induced emission-enhanced luminescent materials.

Objective: This study aimed to explore the clinical features of moyamoya disease (MMD) and the efficacy of encephaloduroarteriosynangiosis (EDAS) in elderly patients with MMD and to identify the risk factors for long-term stroke events., Methods: Clinical data were retrospectively collected on elderly patients with MMD (age ≥ 60 years) who had been treated at the authors' center from May 2007 to December 2017. Clinical features, angiographic findings, and long-term outcomes (> 5-year follow-up) were analyzed. Cox regression analysis was performed to determine the risk factors for postoperative stroke events. Long-term stroke events were analyzed using Kaplan-Meier curves., Results: The mean age at symptom onset was 62.9 ± 3.0 years among 111 elderly patients with MMD. Vascular comorbidities were present in 80 (72.1%) patients. The ratio of female to male patients was 1:1.2. Familial MMD was found in 7 (6.3%) patients. Cerebral ischemia was the most common clinical manifestation observed in 82 (73.9%) patients. Most patients (59.5%) presented with Suzuki stages 5 and 6 MMD, and 29 (26.1%) patients presented with stenosis or occlusion of the posterior circulation. Unilateral MMD was present in 17 (15.3%) patients. Among the 58 (52.3%) patients who underwent EDAS, 28 (48.3%) and 30 (51.7%) underwent bilateral and unilateral surgeries, respectively. Overall, 53 (47.7%) patients were treated conservatively using internal medicine. After a median follow-up duration of 8.2 years, stroke incidence in the EDAS and conservative treatment groups was respectively 17.2% (7 and 3 cases of cerebral infarction and hemorrhage, respectively) and 49.1% (22 and 4 cases of cerebral infarction and hemorrhage, respectively). The stroke incidence rate was higher in the conservative group than in the EDAS group, with a statistically significant difference (p = 0.001) according to results of the Kaplan-Meier analysis. The identified predictor of postoperative stroke events was initial hemorrhage in the EDAS group and advanced age, aneurysm, and initial ischemia in the conservative treatment group., Conclusions: The postoperative long-term stroke rate among elderly patients with MMD was lower in the EDAS group than in the conservative treatment group. Long-term stroke events were associated with advanced age, aneurysm, and initial ischemia after conservative treatment and only initial hemorrhage after EDAS.

Objective: To investigate the impact of prenatal and early childhood antimicrobial use on autism spectrum disorders (ASD)., Data Sources: We searched PubMed and Embase databases for relevant studies from inception to August 2022., Study Selection and Data Extraction: Peer-reviewed, observational studies were all acceptable. Raw data were extracted into a predefined worksheet and quality analysis was performed using the Newcastle-Ottawa Scale., Data Synthesis: Nineteen studies were identified in the meta-analysis. Prenatal antimicrobial exposure was not associated with ASD ( P = 0.06 > 0.05), whereas early childhood antimicrobial exposure was associated with an increased odds ratio of ASD (OR = 1.17, 95% CI = [1.08-1.27], P value < 0.001). The sibling-matched analysis, with a very limited sample size, suggested that neither prenatal ( P = 0.47 > 0.05) nor early childhood ( P = 0.13 > 0.05) antimicrobial exposure was associated with ASD. Medical professionals may need to take the possible association into consideration when prescribing an antimicrobial in children., Conclusions: Early childhood antimicrobial exposure could increase the incidence of ASD. In future studies, it would be necessary to control for confounding factors, such as genetic factors, parenteral age at birth, or low birthweight, to further validate the association.

Background: Spontaneous low-frequency oscillations (LFOs) have been widely studied in cerebrovascular disease, but little is known about their role in moyamoya disease (MMD). The objective of this study was to assess the value of spontaneous LFOs in MMD based on wavelet analysis of near-infrared spectroscopy signals., Methods: Sixty-four consecutive idiopathic adult patients were prospectively enrolled. The regional tissue oxygenation index (TOI) obtained from continuous near-infrared spectroscopy signals. Five frequency intervals of spontaneous LFOs (I, 0.0095-0.02 Hz; II, 0.02-0.06 Hz; III, 0.06-0.15 Hz; IV, 0.15-0.40 Hz; and V, 0.40-2.00 Hz) were extracted based on wavelet analysis. The data were compared between the patients and healthy control groups. Clinical features, cognitive function, and disease progression of MMD were analyzed using TOI and frequency interval data., Results: Compared with the healthy control group, patients with MMD had a higher cerebral TOI in both hemispheres. Based on wavelet analysis, the spontaneous LFO of TOI was found to be significantly lower for patients with MMD in frequency intervals II to IV than that for the controls. The spontaneous LFO of TOI is also related to the Suzuki stages in intervals II to IV, stroke in interval III, and cognitive impairment in intervals III to Ⅳ., Conclusions: There were significant differences in spontaneous LFO between patients with MMD and healthy controls. The change in spontaneous LFO in MMD is related to Suzuki stage, cerebral infarction, and cognitive impairment. This might be an effective method for evaluating the severity and monitoring the progression of MMD., (Copyright © 2022. Published by Elsevier Inc.)

The influence of hypoperfusion on cognition in patients with Moyamoya disease (MMD) is unclear. This study investigated cognitive function changes in MMD patients without stroke and illustrated the relationship between cognitive impairment and hypoperfusion. We prospectively performed a structured battery of seven neurocognitive tests on 115 adult MMD patients without stroke and 82 healthy controls. Hemodynamic assessment was performed using dynamic susceptibility contrast-enhanced MRI. The best subset regression (BSR) strategy was used to identify risk factors. Global cognition (MoCA), speed of information processing (TMT-A), executive function (TMT-B), visuospatial function (CDT), and verbal memory (CAVLT) were significantly poorer in MMD patients without stroke than in healthy controls. The TMT-B score significantly correlated with cerebral blood flow (CBF) in the bilateral lateral frontal lobes, centrum semiovale, and temporal lobes. The TMT-A and CAVLT scores significantly correlated with CBF in the left centrum semiovale (L-CSO) and temporal lobes. According to the BSR results, age, education, white matter lesions, and hypoperfusion of the L-CSO were risk factors for cognitive impairment. Hypoperfusion leads to multiple cognitive impairments in MMD patients without stroke. The perfusion of particular areas may help evaluate the cognitive function of MMD patients and guide therapeutic strategies.

Background and Objective: The natural course and risk factors of moyamoya disease (MMD) associated with unruptured intracranial aneurysms involving stenosed parental arteries are scarcely studied. This study aimed to elucidate the natural course of MMD and its associated risk factors in patients with MMD with unruptured aneurysms., Methods: Between September 2006 and October 2021, patients with MMD with intracranial aneurysms at our center were examined. The natural course, clinical features, radiological features, and follow-up outcomes after revascularization were analyzed., Results: This study included 42 patients with MMD with intracranial aneurysms (42 aneurysms). The age distribution of MMD cases ranged from 6 to 69 years, with four children (9.5%) and 38 adults (90.5%). A total of 17 male and 25 female subjects were included (male-to-female ratio: 1:1.47). The first symptom was cerebral ischemia in 28 cases, and cerebral hemorrhage occurred in 14 cases. There were 35 trunk aneurysms and seven peripheral aneurysms. There were 34 small aneurysms (<5 mm) and eight medium aneurysms (5-15 mm). During the average clinical follow-up period of 37.90 ± 32.53 months, there was no rupture or bleeding from aneurysms. Twenty-seven of these patients underwent a cerebral angiography review, in which it was found that one aneurysm had enlarged, 16 had remained unchanged, and 10 had shrunk or disappeared. A correlation exists between the reduction or disappearance of aneurysms and the progression of the Suzuki stages of MMD ( P = 0.015). Nineteen patients underwent EDAS on the aneurysm side, and nine aneurysms disappeared, while eight patients did not undergo EDAS on the aneurysm side and one aneurysm disappeared., Conclusion: The risk of rupture and hemorrhage of unruptured intracranial aneurysms is low when the parent artery already has stenotic lesions, thus, direct intervention may not be necessary for such aneurysms. The progression of the Suzuki stage of moyamoya disease may play a role in the shrinkage or disappearance of the aneurysms, thereby decreasing the risk of rupture and hemorrhage. Encephaloduroarteriosynangiosis (EDAS) surgery may also help promote atrophy or even the disappearance of the aneurysm, thus reducing the risk of further rupture and bleeding., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 Yang, Hao, Zhao, Zhang, Yu, Zou, Gao, Guo, Shen, Fu, Liu, Wang, Li and Han.)

Objective: Emerging evidence suggests that acupuncture plays a neuroprotective role in autism. This study aimed to explore the effect of electroacupuncture at Zusanli (ST36) on autistic-like behaviors and the underlying mechanism., Method: Pregnant rats were administered with valproic acid (VPA) on gestational day 12.5 to induce an autism spectrum disorder (ASD) model. The pups were given electroacupuncture at ST36 daily from postnatal day (PND) 28-48. On PND28, the adenoviral vector containing small interfering RNA Nrf2 (Ad-siRNA-Nrf2) was injected into the prefrontal cortex of rats. The behavioral analysis was performed on PND 44-48. On PND48, the animals were euthanized and the brains were collected for further detection. Nissl staining was performed to detect neuronal viability. The biochemical markers of oxidative stress were subsequently measured., Result: Electroacupuncture at ST36 ameliorated the locomotor activity, social behavior, spatial learning and memory and repetitive behavior compared with ASD rats. It was notable that the electroacupuncture decreased oxidative stress markers in the tissues of prefrontal cortex, enhanced translocation of nuclear factor erythroid2-related factor2 (Nrf2) from cytoplasm to nucleus, and up-regulated the levels of NADP(H) quinone oxidoreductase (NQO1) and heme oxygenase (HO-1). However, these effects induced by electroacupuncture at ST36 were abolished after injection of Ad-siRNA-Nrf2., Conclusion: These data suggested that electroacupuncture at ST36 protected nerve function in ASD rats through Nrf2 activation and the antioxidant response., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Metal-organic gels (MOGs) are attracting increasing attention for removal of organic dyes from aqueous solution and for catalysis of Si-H insertion reactions. Herein, we report that a reaction of porphyrin derivative 1 with Rh 2 (OAc) 4 generates stable metal-organic gels and subsequent subcritical carbon dioxide drying affords metal-organic aerogels. Owing to their micro- and mesoporosity, the aerogels adsorbed dyes. Moreover, aerogel I catalyzed Si-H insertion reactions to give organosilicon compounds in high yields., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Intelligent fluorescent materials have been paid more and more attention due to their wide application in information encryption and anti-counterfeiting materials. Herein, a supramolecular polymer is constructed through the host-guest interaction of anthraquinone-modified β -cyclodextrin (AQ- β -CD) in aqueous solution. Thanks to the hydrophobic microenvironment of the cyclodextrin cavity and the shielding effect on oxygen molecules, the anthraquinone group, as the guest molecule, can rapidly produce 9,10-anthracenediol (QH 2 ) with strong fluorescence by photoreduction. Interestingly, the generated anthracenediol group is still sensitive to oxygen and can be converted to anthraquinone by oxygen. Significantly, aqueous solution of AQ- β -CD supermolecular polymer is used as emitting ink, which decrypts the information by ultraviolet light and encrypts the information in the air., Competing Interests: The authors declare no conflict of interest., (© 2020 The Authors. Published by WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.)

A novel two-step in situ method for targeted antitumor drug release by supramolecular assembly (Fc-CPT@HACD) was constructed using camptothecin prodrug (Fc-CPT) and β-cyclodextrin (β-CD)-modified hyaluronic acid (HACD). Benefiting from the overexpressed H 2 O 2 and glutathione (GSH) in tumor cells, Fc-CPT@HACD can be disassembled by oxidation of ferrocene (Fc) to Fc + , leading to an efficient release of the anticancer drug camptothecin (CPT) to induce tumor cell apoptosis without affecting normal cells. The in vivo experiment results also demonstrated that Fc-CPT@HACD possessed higher anticancer efficiency than free CPT, accompanied by negligible side effects., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

Objective: To evaluate the effect of dexmedetomidine on lung injury and CCAAT/enhancer-binding protein homologous protein (CHOP) expression in elderly patients with lung cancer undergoing thoracoscopic lobectomy. Methods: A total of 120 elderly patients with lung cancer who underwent elective thoracoscopic lobectomy were selected from the Second Affiliated Hospital of Zhengzhou University from October 2018 to March 2019. The random phenotype was divided into dexmedetomidine group (group D, n= 60) and control group (group C, n= 60). The elapsed time before postoperative awake and spontaneous breathing recovery and agitation occurrence were recorded. The mean arterial pressure (MAP), heart rate (HR), oxygen saturation (SPO(2)), oxygen partial pressure (PaO(2)), alveolar-arterial oxygen partial pressure difference[P(A-a)O(2)], end-tidal carbon dioxide partial pressure (P(ET)CO(2)), and airway pressure peak (P(peak)) were recorded before the anesthetic induction (T(0)), immediately after tracheal intubation (T(1)), immediately after unilateral pulmonary ventilation(T(2)), 1 hour after unilateral pulmonary ventilation (T(3)), immediately after bilateral pulmonary ventilation (T(4)), and at the end of surgery(T(5)). The levels of tumor necrosis factor-α (TNF-α), interleukin-6 (IL-6), IL-8, IL-10, super oxide dismutase (SOD) and malondialdehyde (MDA)were compared at the time of T(0), T(1), T(2), T(3), T(4) and T(5) in two groups. The ratios of alveolar damage (IQA), apoptotic index (AI), and the expression of CHOP mRNA and their protein in lung tissue were detected. Results: The recovery time of conscious and spontaneous breathing in group D were significantly shorter than that in group C ( P< 0.05). The MAP and HR of the two groups at T(1)-T(5) were significantly lower than those at T(0)( P< 0.05).The levels of P(peak) in group C at T(3)-T(5) was significantly higher than those in group D ( P< 0.05). The SpO(2) values in the group D at T(1)-T(5) were significantly higher than those in group C ( P< 0.05). The P(A-a)O(2) values in the group D at T(1)-T(5) was significantly lower than those in group C ( P< 0.05).The levels of IL-6, IL-8 and MDA in group D at T(1)-T(5) were significantly lower than those in group C( P< 0.05). The levels of IL-10 and SOD in group D at T(1)-T(5) were significantly higher than those in group C ( P< 0.05). The values of IQA, AI, and the expression of CHOP mRNA and their protein in the two groups at T(4) were significantly higher than those at T(2) ( P< 0.05). The values of IQA, AI, and the expression of CHOP mRNA and their protein in group D at T(4) were significantly lower than those in group C ( P< 0.05). Conclusions: Dexmedetomidine could attenuate the extent of lung injury in elderly patients with lung cancer undergoing thoracoscopic lobectomy. The pulmonary protective mechanism could be related to the inhibition of inflammatory factors in dexmedetomidine, improving oxidative stress and reducing Chop-mediated apoptosis of lung tissue by the protein.

Based on the structural characteristics of aztreonam (AZN) and its target PBP3, a series of new monobactam derivatives bearing various substituents on oxime residue were prepared and evaluated for their antibacterial activities against susceptible and resistant Gram-negative bacteria. Among them, compounds 8p and 8r displayed moderate potency with MIC values of 0.125-32 μg/mL against most tested Gram-negative strains, comparable to AZN. Meanwhile, the combination of 8p and 8r with avibactam as a β-lactamases inhibitor, in a ratio of 1:16, showed a promising synergistic effect against both ESBLs- and NDM-1-producing K. pneumoniae, with significantly reduced MIC values up to 8-fold and >256-fold respectively. Furthermore, both of them demonstrated excellent safety profiles both in vitro and in vivo. The results provided powerful information for further structural optimization of monobactam antibiotics to fight β-lactamase-producing resistant Gram-negative bacteria., (Copyright © 2019 Elsevier Inc. All rights reserved.)

The use of light to regulate the chirality of supramolecular assemblies in a non-invasive manner remains a challenge. Herein, we report a novel photochromic pseudo[3]rotaxane based on a (R/S)-2,2'-binaphthyl secondary ammonium salt guest (2) and anthracene-bridged bis(dibenzo-24-crown-8) (1), which features a chirality transfer and fluorescence resonance energy transfer (FRET) from 2 to 1. Benefiting from the photo-oxidation of anthracene, the induced circular dichroism (ICD) signals of (R/S)-2@1 can be switched off/on by irradiation with 365 nm UV light and heating. This noncovalent supramolecular assembly strategy provides us with unique opportunities to design and construct further smart photo-responsive chiral molecular switches.

A novel multistimuli-responsive and photcontrolled supramolecular luminescent gel is fabricated from anthracene-bridged bis(dibenzo-24-crown-8) (1) and secondary ammonium salt-functionalized graft polymer (3). X-ray crystallographic analysis reveals that the dibenzo-24-crown-8 (DB24C8) ring is located at the opposite site of 1, which will greatly hinder the mutual intermolecular π-π stacking between anthracene groups. By taking advantage of the controllable binding of 1 with 3, the unique gel-sol transition could occur under different temperatures, pH, and competitive guest bindings. Benefiting from the photo-oxygenation of anthracene, the luminescence behavior of the supramolecular gel could be switched off and on under UV light (365 nm) and heating treatment, which provides a new approach for constructing photocontrolled supramolecular luminescent gel.

Supramolecular assembly with tumor-targeting properties or photodynamic therapy (PDT) ability has recently become a focus of interest in biomaterial field because of its high therapeutic efficacy against tumor cells. Herein, we reported a new type of targeted supramolecular nanoparticles for photodynamic therapy of tumor cells constructed using adamantane-functionalized transferrin protein (Ad-TRF) and a β-cyclodextrin-functionalized ruthenium complex (Ru-HOP-CD), wherein Ad-TRFs acted as the targeted sites for tumor cells, the coordinated Ru(ii) centers acted as the PDT active sites, and the biocompatible polysaccharide β-cyclodextrins acted as the non-covalent linkers. Significantly, the resultant Ru/polysaccharide/protein exhibited not only specific targeting properties towards tumor cells but also high PDT ability under the irradiation of visible light. Furthermore, the assembly showed selective killing towards tumor cells along with negligible toxicity towards normal cells.

Nineteen new quinoline derivatives were prepared via the Mannich reaction and evaluated for their antibacterial activities against both Gram-positive (G⁺) and Gram-negative (G - ) bacteria, taking compound 1 as the lead. Among the target compounds, quinolone coupled hybrid 5d exerted the potential effect against most of the tested G⁺ and G - strains with MIC values of 0.125⁻8 μg/mL, much better than those of 1 . Molecular-docking assay showed that compound 5d might target both bacterial LptA and Top IV proteins, thereby displaying a broad-spectrum antibacterial effect. This hybridization strategy was an efficient way to promote the antibacterial activity of this kind, and compound 5d was selected for the further investigation, with an advantage of a dual-target mechanism of action.

Objective: To observe and evaluate the effect of dexmedetomidine on the perioperative immune function of patients undergoing a radical mastectomy., Patients and Methods: 124 patients undergoing radical mastectomy were divided into the observation group (treated with dexmedetomidine) and the control group (treated with saline) by randomized digital table and double blinded and randomized design. 10 min before anesthesia induction, the patients in the observation group were injected with dexmedetomidine 0.1 ug.kg-1.min-1. The injection of 0.9% sodium chloride solution was given to the control group at the same rate. In the experiment, the medications of anesthesia induction and anesthesia maintain were identical. Venous blood at five times: T0 (before anesthesia), T1 (6 h after surgery), T2 (24 h after surgery), T3 (48 h after surgery), T4 (72 h after surgery) were collected. ELISA (Enzyme Linked Immunosorbent Assay) was used to detect concentrations of IL-2, IFN-γ, IL-4, IL-6 and IL-10; FACS flow cytometry was used to determine the level of T-lymphocyte subsets (CD3+, CD4+, CD8+) and NK cells., Results: Compared with the control group, the cell levels of CD3+ and CD4+ in the observation group rose remarkably at T3 and T2 (p<0.05). The cell level of CD8+ fell at T2 with significant difference; NK cell level increased noticeably at T1 and T2, and CD4+/CD8+ rose dramatically at all postoperative time points. Obviously, the patients' immune function, to some extent, has been affected; in addition, the concentration of INF-γ in observation group increased prominently at T1, T2 and T3 (p<0.05), and the concentration of IL-2 at T2, IL-10 at T1 and T2, and IL-6 at T2 and T3 in the observation group all rose significantly (p<0.05), and less cytokine Th1 drifted to Th2., Conclusions: The dexmedetomidine can effectively maintain the homeostasis of cell immune function of patients undergoing a radical mastectomy.

A series of monobactam derivatives were prepared and evaluated for their antibacterial activities against susceptible and resistant Gram-negative strains, taking Aztreonam and BAL30072 as the leads. Six conjugates (12a-f) bearing PIH-like siderophore moieties were created to enhance the bactericidal activities against Gram-negative bacteria based on Trojan Horse strategy, and all of them displayed potencies against susceptible Gram-negative strains with MIC ≤ 8 μg/mL. SAR revealed that the polar substituents on the oxime side chain were beneficial for activities against resistant Gram-negative bacteria. Compounds 19c and 33a-b exhibited the promising potencies against ESBLs-producing E. coli and Klebsiella pneumoniae with MICs ranging from 2 μg/mL to 8 μg/mL. These results offered powerful information for further strategic optimization in search of the antibacterial candidates against MDR Gram-negative bacteria., (Copyright © 2016 Elsevier Masson SAS. All rights reserved.)

Background: This study investigated the influence of human cytochrome P450 2D6 (CYP2D6) gene polymorphism in gastric cancer (GC) patients to understand the pharmacogenomic basis for patient response to postoperative fentanyl analgesia., Methods: The prospective study design contained 212 patients recovering from radical gastrectomy. Peripheral blood samples were collected after general anesthesia, and CYP2D6 genotypes were analyzed using polymerase chain reaction-restriction fragment length polymorphism (PCR-RFLP) method. After providing adequate instructions to operate the analgesia pump, patients self-administered fentanyl via patient controlled intravenous analgesia. The cumulative amount of fentanyl self-administered and the associated adverse effects were recorded at 6, 12, 24, and 48 h postoperatively., Results: Five patients, out of the 212 patients recruited to this study, failed to complete the study. The remaining 207 patients were classified into three groups based on their genotypes: W/W group (n=44), M/W group (n=112), and M/M group (n=51). Our results demonstrated that the cumulative amount of fentanyl consumption significantly increased in the M/M group at 6, 12, and 24 h postoperatively, compared with the W/W group (p<0.05). In addition, visual analogue scale (VAS) score in the M/M group was significantly higher than the W/W group in the analepsia period after general anesthesia and at 6 h postoperatively (p<0.05). No significant adverse effects were observed in all the groups (p>0.05)., Conclusion: CYP2D6 polymorphism influenced patient response to postoperative fentanyl analgesia in GC patients.

Waste cornstalks and pomelo skins are used as carbon resources for preparing nanocomposites of iron oxide and partly graphitized carbon (Fe3O4/PGC-CS and Fe3O4/PGC-PS). The results showed that Fe3O4 with a face-centered cubic structure is uniformly dispersed on the skeleton of Fe3O4/GC, and the highest SBET values of Fe3O4/PGC-CS (476.5 m(2) g(-1)) and Fe3O4/PGC-PS (547.7 m(2) g(-1)) are obtained at 1000 °C. The electrical conductivity and density of catalytic active sites are correspondingly improved by the introduction of Fe species. Microbial fuel cells (MFCs) with a mixed composite (Fe3O4/PGC-CS:Fe3O4/PGC-PS = 1:1) cathode (three-dimensional structures) generate the highest power density of 1502 ± 30 mW m(-2), which is 26.01% higher than that of Pt/C (1192 ± 33 mW m(-2)) and only declines by 7.12% after 18 cycles. The Fe3O4/PGC-CS cathode has the highest Coulombic efficiency (24.3 ± 0.7%). The Fe3O4/PGC composites exhibit high oxygen reduction reactivity, low charge transfer resistances, and long-term stability and can be used as a low-cost and high-efficiency catalyst for MFCs.

The removal of dyes in wastewater has been of much interest in the recent decades because dyes are stable, toxic and even potentially carcinogenic, and their release into environment causes serious environmental, aesthetical, and health problems. In the current work, indium-based coordination polymer particles (In-CPPs) have been fabricated via a facile solvothermal synthesis without any template or surfactant. In-CPPs are composed of hierarchical nanostructures assembled from abundant nanoplates with thickness of about 20 nm. Owing to their high BET surface area and pore volume, In-CPPs exhibit excellent adsorption capability for Congo red with a maximum capacity of 577 mg g(-1), which was higher than that of most materials reported to now. In-CPPS can also be outstanding adsorbents for removing other dyes such as acid chrome blue K, brilliant red GR and brilliant green. Furthermore, after calcinations in air In-CPPs can be converted to morphology-preserved porous In2O3 products which can detect NOx gas in air at room temperature., (Copyright © 2014 Elsevier Inc. All rights reserved.)

Background: The emergence of multi-drug resistant tuberculosis (MDR-TB) has heightened the need for new chemical classes and innovative strategies to tackle TB infections. It is urgent to discover new classes of molecules without cross-resistance with currently used antimycobacterial drugs., Results: Eighteen new 8-substituted protoberberine derivatives were synthesized and evaluated for their anti-mycobacterial activities against Mycobacterium tuberculosis (M. tuberculosis) strain H37Rv. Among them, compound 7g was the most effective antitubercular agent with minimum inhibitory concentration (MIC) of 0.5 μg/mL. Moreover, it also afforded a potent antitubercular effect against clinically isolated MDR strains of M. tuberculosis with MICs ranging from 0.25 to 1.0 μg/mL, suggesting a novel mode of action., Conclusions: The structure-activity relationship (SAR) analysis revealed that introduction of a substituent at the 8-position in pseudoprotoberberine, especially an n-decyl, could significantly enhance the anti-TB activity. We consider 8-n-decylberberines to be a novel family of anti-tubercular agents with an advantage of inhibiting MDR strains of M. tuberculosis.

Exploring and evaluating the potential applications of two-dimensional graphene is an increasingly hot topic in graphene research. In this paper, by studying the adsorption of NO, N(2)O, and NO(2) on pristine and silicon (Si)-doped graphene with density functional theory methods, we evaluated the possibility of using Si-doped graphene as a candidate to detect or reduce harmful nitrogen oxides. The results indicate that, while adsorption of the three molecules on pristine graphene is very weak, Si-doping enhances the interaction of these molecules with graphene sheet in various ways: (1) two NO molecules can be adsorbed on Si-doped graphene in a paired arrangement, while up to four NO(2) molecules attach to the doped graphene with an average adsorption energy of -0.329 eV; (2) the N(2)O molecule can be reduced easily to the N(2) molecule, leaving an O-atom on the Si-doped graphene. Moreover, we find that adsorption of NO and NO(2) leads to large changes in the electronic properties of Si-doped graphene. On the basis of these results, Si-doped graphene can be expected to be a good sensor for NO and NO(2) detection, as well as a metal-free catalyst for N(2)O reduction.

Scalar relativistic density functional theory (DFT) has been used to explore the spectroscopic and redox properties of Ruthenium-type photovoltaic sensitizers, trans-[Ru((R)L)(NCS)(2)] ((R)L = 4,4'''-di-R-4',4''-bis(carboxylic acid)-2,2' : 6',2'' : 6'',2'''-quaterpyridine, R = H (1), Me (2), (t)Bu (3) and COOH (4); (R)L = 4,4'''-di-R-4',4''-bis(carboxylic acid)-cycloquaterpyridine, R = COOH (5)). The geometries of the molecular ground, univalent cationic and triplet excited states of 1-5 were optimized. In complexes 1-4, the quaterpyridine ligand retains its planarity in the molecular, cationic and excited states, although the C≡N-Ru angle representing the SCN → Ru coordination approaches 180° in the univalent cationic and triplet excited states. The theoretically designed complex 5 displays a curved cycloquaterpyridine ligand with significantly distorted SCN → Ru coordination. The electron spin density distributions reveal that one electron is removed from the Ru/NCS moieties upon oxidation and the triplet excited state is due to the Ru/NCS → polypyridine charge transfer (MLCT/L'LCT). The experimental absorption spectra were well reproduced by the time-dependent DFT calculations. In the visible region, two MLCT/L'LCT absorption bands were calculated to be at 652 and 506 nm for 3, agreeing with experimental values of 637 and 515 nm, respectively. The replacement of the R- group with -COOH stabilizes the lower-energy unoccupied orbitals of π* character in the quaterpyridine ligand in 4. This results in a large red shift for these two MLCT/L'LCT bands. In contrast, the lower-energy MLCT/L'LCT peak of 5 nearly disappears due to the introduction of cycloquaterpyridine ligand. The higher energy bands in 5 however become broader and more intense. As far as absorption in the visible region is concerned, the theoretically designed 5 may be a very promising sensitizer for DSSC. In addition, the redox potentials of 1-5 were calculated and discussed, in conjunction with photosensitizers such as cis-[Ru(L(1))(2)(X)(2)] (L(1) = 4,4'-bis(carboxylic acid)-2,2'-bipyridine; X = NCS(-) (6), Cl(-) (7) and CN(-) (8)), cis-[Ru(L(1)')(2)(NCS)(2)] (L(1)' = 4,7-bis(carboxylic acid)-1,10-phenanthroline, 9), [NH(4)][Ru(L(2))(NCS)(3)] (L(2) = 4,4',4''-tris(carboxylic acid)-2,2' : 6',2''-terpyridine, 10) and [Ru(L(2))(NCS)(3)](-) (11).

The structural and electronic properties of five terminations of cubic lead titanate (PbTiO3) (110) polar surface were investigated by first-principles total-energy calculations using a periodic slab model. On the PbTiO termination, an anomalous filling of conduction band was observed, whereas on the O2 termination, two surface oxygen atoms formed a peroxo group, demonstrating that the electronic structures of the two stoichiometric terminations undergo significant changes with respect to bulk materials. However, for the three nonstoichiometric TiO-, Pb-, and O-terminated surfaces, their electronic structures are very similar to bulk. Charge redistribution results for the five terminations confirmed that electronic structure and surface composition changes are responsible for their polarity compensation. However, which mechanism actually dominates the stabilization process depends upon energetic considerations. A thermodynamic stability diagram suggested that the two stoichiometric terminations are unstable; however, the three nonstoichiometric terminations can be stabilized in some given regions. Furthermore, this study indicates that the very different stabilities and surface states filling behaviors of the PbTiO3 (110) polar surface with respect to SrTiO3 and BaTiO3 ones seem to originate from the partially covalent characteristics of Pb-O pairs., (Copyright 2008 Wiley Periodicals, Inc.)

To understand their photocatalytic activity and application in luminescent materials, a series of gold and rhodium phosphine complexes (mononuclear [Au(I)(PH(3))(2)](+) (1) and [Rh(I)(CNH)(2)(PH(3))(2)](+) (2); homobinuclear [Au(I)(2)(PH(2)CH(2)PH(2))(2)](2+) (3) and [Rh(I)(2)(CNH)(4)(PH(2)CH(2)PH(2))(2)](2+) (4); heterobinuclear [Au(I)Rh(I)(CNH)(2)(PH(2)CH(2)PH(2))(2)](2+) (5), [Au(I)Rh(I)(CNH)(2)(PH(2)NHPH(2))(2)Cl(2)] (6), and [Au(I)Rh(I)(CNH)(2)(PH(2)NHPH(2))(2)](2+) (7); and oxidized derivatives [Au(II)Rh(II)(CNH)(2)(PH(2)CH(2)PH(2))(2)](4+) (8), [Au(II)Rh(II)(CNH)(2)(PH(2)NHPH(2))(2)Cl(3)](+) (9), and [Au(II)Rh(II)(CNH)(2)(PH(2)NHPH(2))(2)](4+) (10)) were investigated using ab initio methods and density functional theory. With the use of the MP2 method, the M-M' distances in 3-7 were estimated to be in the range of 2.76-3.02 A, implying the existence of weak metal-metal interaction. This is further evident in the stretching frequencies and bond orders of M-M'. The two-electron oxidation from 5-7 to their respective partners 8-10 was shown to mainly occur in the gold-rhodium centers. Experimental absorption spectra were well reproduced by our time-dependent density functional theory calculations. The metal-metal interaction results in a large shift of d(z(2)) --> p(z) transition absorptions in binuclear complexes relative to mononuclear analogues and concomitantly produces a low-lying excited state that is responsible for increasing visible-light photocatalytic activities. Upon excitation, the metal-centered transition and the metal-to-metal charge transfer strengthen the metal-metal interaction in triplet excited states for 3-6, while the promotion of electrons into the sigma*(d(z(2))) orbital weakens the interaction in 9.

The well-aligned ZnO nanorod arrays were fabricated through a simple chemical process under low temperature. The nanorod arrays were characterized by XRD, SEM, TEM, HRTEM and SAED, and their optical performances were investigated with Raman and PL spectroscopy. The results show that the as-prepared ZnO nanorod arrays are dense, the individual ZnO nanorod is hexagonal shape and grows along c-axis perpendicular to the substrate surface with good single crystal in nature. The Raman property of nanorod arrays displays change with the altering the preparation conditions. Moreover, the PL performances of ZnO nanorod arrays exhibit tunable character with adjusting the synthesis conditions.

A series of ruthenium(II) complexes, [Ru(tcterpy)(NCS)3](4-) (0H), [Ru(Htcterpy)(NCS)3](3-) (1H), [Ru(H2tcterpy)(NCS)3](2-) (2H), and [Ru(H3tcterpy)(NCS)3](-) (3H) (tcterpy = 4,4',4''-tricarboxy-2,2':6',2''-terpyridine), are investigated theoretically to explore their electronic structures and spectroscopic properties. The geometry structures of the complexes in the ground and excited states are optimized by the density functional theory and single-excitation configuration interaction methods, respectively. The absorption and emission spectra of the complexes in gas phase and solutions (ethanol and water) are predicted at the TDDFT(B3LYP) level. The calculations indicate that the protonation effect slightly affects the geometry structures of the complexes in the ground and excited states but leads to significant change in the electronic structures. In cases of both absorptions and emissions, the energy levels of HOMOs and LUMOs for 0H-3H decrease dramatically as a result of the introduction of the COOH groups. The protonation much stabilizes the unoccupied orbitals with respect to the occupied orbitals. Thus, both the absorptions and emissions are red-shifted from 0H to 3H. The phosphorescence of 0H-3H are attributed to tcterpyridine --> d(Ru)/NCS ((3)MLCT/(3)LLCT) transitions. The solvent media can influence the molecular orbital distribution of the complexes; as a consequence, the spectra calculated in the presence of the solvent are in good agreement with the experimental results. The MLCT/LLCT absorptions of 0H in ethanol and water are red-shifted relative to that in the gas phase. However, the MLCT/LLCT absorptions of the protonated complexes (1H-3H) are blue-shifted in ethanol and water with respect to the gas phase. Similarly, the solvent effect causes a blue-shift of the phosphorescent emission for 0H-3H.

A theoretical study on the protonation system of [N,C,C,S], [H,N,C,C,S]+, was performed at the B3LYP/6-311++G(d,p) and CCSD(T)/6-311++G(2df,2p) (single point) levels of theory. On the doublet [H,N,C,C,S]+ surface, 24 species were located as energy minima and 10 of them were considered as kinetically stable species. The species HNCCS+ with 2A' state and a shallow W-shaped skeleton was predicted to be the global minimum and kinetically the most stable species, being in good agreement with previous experimental findings. Furthermore, the protonation reactions of the stable [N,C,C,S] isomers were investigated in detail. The calculation results indicated that the [N,C,C,S] isomers may be significantly stabilized upon protonation. Finally, the possible covalent structures of the [H,N,C,C,S]+ isomers with considerable stability were briefly discussed., (Copyright (c) 2007 Wiley Periodicals, Inc.)

The possible reaction product distribution and mechanism of carbon monophosphide CP with unsaturated hydrocarbons allene CH(2)CCH(2) and methylacetylene CH(3)CCH are investigated at the B3LYP/6-311+G(d,p), QCISD(T)/6-311++G(2df,2p), and G2 levels of theory. Corresponding reactants, products, intermediates, and interconversion and dissociation transition states are located on the reaction potential energy profiles. Computation results show that in the reaction of CP with CH(2)CCH(2) the dominant reaction product should be species CH(2)CCHCP. Also, we can suggest species HCCCH(2)CP as a secondary reaction product despite of only minor contribution to reaction products. In the reaction of CP with CH(3)CCH, the primary and secondary products are suggested to be two important molecules HCCCP and CH(3)CCCP, respectively. The predicted mechanisms for the two reactions are not in parallel with the reactions of CN with allene CH(2)CCH(2) and methylacetylene CH(3)CCH given in previous studies. The present calculations provide some useful information for future possible experimental isolation and observation for some interesting unsaturated carbon-phosphorus-bearing species.

The structures of trans-[M(2)(CN)(4)(PH(2)CH(2)PH(2))(2)] (M = Pt (1), Pd (2), and Ni (3)), trans-[Pt(2)X(4)(PH(2)CH(2)PH(2))(2)] (X = Cl (4) and Br (5)), and trans-[M(CN)(2)(PH(3))(2)] (M = Pt (6), Pd (7), and Ni (8)) in the ground state were optimized using the MP2 method. Frequency calculations reveal that the weak metal-metal interaction is essentially attractive for 1, 2, 4, and 5 but not for 3. The TD-DFT calculations associated with the polarized continuum model (PCM) were performed to predict absorption spectra in CH(2)Cl(2) solution. Experimental spectra are well reproduced by our results. With respect to analogous mononuclear d(8) complexes (6-8), a large red shift of the absorption wavelength was calculated for the binuclear d(8) complexes (1-3). Relative to 1 with unsaturated CN- donors, introduction of saturated halogen donors into 4 and 5 changes their electronic structures, especially the HOMO and LUMO. The TD-DFT and subsequent unrestricted MP2 calculations predict that 1 produces the lowest-energy d --> p emission while 2-5 favor the d --> d emissions, agreeing with experimental observations.

The structures of [Pt2(pop)4]4-, [Pt2(pcp)4]4-, and related species [Pt2(pop)4X2]4- and [Pt2(pop)4]2- in the ground states (pop = P2O5H2(2-), pcp = P2O4CH4(2-), and X = I, Br, and Cl) were optimized using the second-order Møller-Plesset perturbation (MP2) method. It is shown that the Pt-Pt distances decrease in going from [Pt2(pop)4]4- to [Pt2(pop)4X2]4- to [Pt2(pop)4]2-. This is supported by the analyses of their electronic structures. The calculated aqueous absorption spectra at the time-dependent density functional theory (TD-DFT) level agree with experimental observations. The unrestricted MP2 method was employed to optimize the structures of [Pt2(pop)4]4- and [Pt2(pcp)4]4- in the lowest-energy triplet excited states. The Pt-Pt contraction trend is well reproduced in these calculations. For [Pt2(pop)4]4-, the Pt-Pt distance decreases from 2.905 A in the ground state to 2.747 A in the excited state, which is comparable to experimental values of 2.91-2.92 A and 2.64-2.71 A, respectively. On the basis of the excited-state structures of such complexes, TD-DFT predicts the solution emissions at 480 and 496 nm, which is closer to the experimental values of 512 and 510 nm emissions, respectively.