Co@CoO催化剂表面类氢负物种NH_(2)^(δ-)驱动下的还原胺化反应

胺类化合物作为一类重要的精细化学品,广泛应用于合成染料、表面活性剂、聚合物、药品和农用化学品.催化还原胺化是合成胺类化合物的重要手段.在还原胺化反应中,水是唯一的副产物,且反应条件温和,符合绿色化学原则,因此受到了广泛关注.在过去的几十年里,生物质衍生的羰基化合物(糠醛、环戊酮、5-羟甲基糠醛等)的催化还原胺化得到了特别关注,为利用可再生资源可持续地生产胺类提供了可能性.通常,金属(Ru,Ir,Pt,Rh,Co,Ni等)被认为是还原胺化的活性中心,相关研究快速发展,但大部分研究都围绕着金属负载型催化剂展开,对于以金属氧化物为活性中心鲜有研究.另外,还原胺化过程研究表明,席夫碱在反应开始阶段迅速生成,然后通过氨解产生相应的伯胺;但席夫碱氨解为伯胺的过程速率较慢,是该反应的决速步骤,因此设计高效催化剂加快席夫碱的氨解是还原胺化过程中的重要科学问题.受孤立的路易斯酸碱对可以催化氢气异裂过程的启发,本文利用具有核壳结构的Co@Co O为催化剂,发现表面具有氧空位的CoO具有独特的解离NH_(3)生成类氢负物种(NH_(2)^(δ-))的能力,该NH_(2)^(δ-)物种能够加速席夫碱的氨解,从而使得该催化剂展现出较好的还原胺化性能,且具有较好的稳定性,在环戊酮胺化为环戊胺过程中使用10次没有失活.通过密度泛函理论(DFT)计算和D_(2)同位素示踪实验发现了类氢负物种NH_(2)^(δ-),且验证了H^(δ-)和NH_(2)^(δ-)物种在Co O表面可稳定地共吸附,席夫碱在催化剂表面吸附较弱,使得希夫碱中间体可以在解离NH_(2)^(δ-)和H^(δ-)后的CoO表面自由移动,从而与表面解离的H^(-)和NH_(2)^(δ)–发生分子碰撞,生成伯胺,最后脱附完成催化循环.本文实现了金属氧化物催化还原胺化反应.更重要的是,在加氢/氢解反应中,孤立的路易斯酸碱对上异裂产生的H^(δ-)物种虽然具有较好的活性,但是没有H^(δ-)物种参与反应直接证据的相关报道,本研究发现的类氢负物种NH_(2)^(δ-)参与胺化反应的证据间接表明了H^(δ-)物种参与加氢/氢解反应的可能性.

Simulation and energy performance assessment of CO_2 removal from crude synthetic natural gas via physical absorption process

The paper presents an energy performance assessment of CO2 removal for crude synthetic natural gas （SNG） upgrade by Selexol absorption process. A simplified process simulation of the Selexol process concerning power requirement and separation performance was developed. The assessment indicates that less pressure difference between crude SNG and absorption pressure favors the energy performance of CO2 removal process. When both crude SNG and absorption pressures are 20 bar, CO2 removal process has the best energy performance. The optimal specific power consumption of the CO2 removal process is 566 kJ/kgCO2. The sensitivity analysis shows that the CO2 removal efficiency would significantly influence the total power consumption of the removal process, as well as higher heating value （HHV） and CO2 content in SNG. However, the specific power consumption excluding crude SNG and SNG compressions changes little with the variance of CO2 removal efficiency. If by-product CO2 is compressed for CO2 capture, the process would turn into a CO2-sink for the atmosphere. Correspondingly, an increase of 281 kJ/kgCO2 in specific power consumption is required for compressing the separated CO2.

Expert consensus on the prevention and treatment of substance use and addictive behaviour-related disorders during the COVID-19 pandemic

In early 2020,the COVID-19 outbreak complicated the diagnosis,treatm ent and rehabilitation of patients with substance use disorders and increased the risks of substance abuse and addictive behaviours,such as online gaming disorders,in the general public.Substance use disorder is a chronic recurrent brain disease characterised by strong cravings,high recurrence rates,and a high proportion of comorbidity of mental and physical disorders.1 Therefore,regular long-term therapeutic interventions are critical to preventing dm g relapses while maintaining withdrawal.

Shared and Distinct Topographic Alterations of Alpha-Range Resting EEG Activity in Schizophrenia,Bipolar Disorder,and Depression

DearEditor,Schizophrenia(SCZ),bipolar disorder(BD),and major depressive disorder(MDD)are common psychiatric disorders that share several characteristics such as risk genes,and cognitive,neural,and structural abnormalities[1-3].Despite this,the boundaries between the three disorders are not clearly defined in clinical practice,and the"crosscutting"dimensional assessment of symptoms and clinical phenomena is controversial[2,4].To improve the classification criteria,it is essential to explore the underlying relationships among these disorders and address the fuzzy divergence that exists.

New role of platelets in schizophrenia:predicting drug response

Background Elevated platelet count(PLTc)is associated with first-episode schizophrenia and adverse outcomes in individuals with precursory psychosis.However,the impact of antipsychotic medications on PLTc and its association with symptom improvement remain unclear.Aims We aimed to investigate changes in PLTc levels following antipsychotic treatment and assess whether PLTc can predict antipsychotic responses and metabolic changes after accounting for other related variables.Methods A total of 2985 patients with schizophrenia were randomised into seven groups.Each group received one of seven antipsychotic treatments and was assessed at 2,4 and 6 weeks.Clinical symptoms were evaluated using the positive and negative syndrome scale(PANSS).Additionally,we measured blood cell counts and metabolic parameters,such as blood lipids.Repeated measures analysis of variance was used to examine the effect of antipsychotics on PLTc changes,while structural equation modelling was used to assess the predictive value of PLTc on PANSS changes.Results PLTc significantly increased in patients treated with aripiprazole(F=6.00,p=0.003),ziprasidone(F=7.10,p<0.001)and haloperidol(F=3.59,p=0.029).It exhibited a positive association with white blood cell count and metabolic indicators.Higher baseline PLTc was observed in non-responders,particularly in those defined by the PANSS-negative subscale.In the structural equation model,PLTc,white blood cell count and a latent metabolic variable predicted the rate of change in the PANSS-negative subscale scores.Moreover,higher baseline PLTc was observed in individuals with less metabolic change,although this association was no longer significant after accounting for baseline metabolic values.Conclusions Platelet parameters,specifically PLTc,are influenced by antipsychotic treatment and could potentially elevate the risk of venous thromboembolism in patients with schizophrenia.Elevated PLTc levels and associated factors may impede symptom improvement by promoting inflammation.Given PLTc’s easy measurement and clinical relevance,it warrants increased attention from psychiatrists.Trial registration number ChiCTR-TRC-10000934.

GABAergic Abnormalities Associated with Sensorimotor Corticostriatal Community Structural Deficits in ErbB4 Knockout Mice and First-Episode Treatment-Naive Patients with Schizophrenia

The current study was designed to explore how disruption of specific molecular circuits in the cerebral cortex may cause sensorimotor cortico-striatal community structure deficits in both a mouse model and patients with schizophrenia.We used prepulse inhibition(PPI)and brain structural and diffusion MRI scans in 23 mice with conditional ErbB4 knockout in parvalbumin interneurons and 27 matched controls.Quantitative real-time PCR was used to assess the differential levels of GABA-related transcripts in brain regions.Concurrently,we measured structural and diffusion MRI and the cumulative contribution of risk alleles in the GABA pathway genes in firstepisode treatment-naı¨ve schizophrenic patients(n=117)and in age-and sex-matched healthy controls(n=86).We present the first evidence of gray and white matter impairment of right sensorimotor cortico-striatal networks and reproduced the sensorimotor gating deficit in a mouse model of schizophrenia.Significant correlations between gray matter volumes(GMVs)in the somatosensory cortex and PPI as well as glutamate decarboxylase 1 mRNA expression were found in controls but not in knockout mice.Furthermore,these findings were confirmed in a human sample in which we found significantly decreased gray and white matter in sensorimotor cortico-striatal networks in schizophrenic patients.The psychiatric risk alleles of the GABA pathway also displayed a significant negative correlation with the GMVs of the somatosensory cortex in patients.Our study identified that ErbB4 ablation in parvalbumin interneurons induced GABAergic dysregulation,providing valuable mechanistic insights into the sensorimotor cortico-striatal community structure deficits associated with schizophrenia.

Age-Related Reduction in Cortical Thickness in First-Episode Treatment-Na?ve Patients with Schizophrenia

Substantial evidence supports the neurodevelopmental hypothesis of schizophrenia.Meanwhile,progressive neurodegenerative processes have also been reported,leading to the hypothesis that neurodegeneration is a characteristic component in the neuropathology of schizophrenia.However,a major challenge for the neurodegenerative hypothesis is that antipsychotic drugs used by patients have profound impact on brain structures.To clarify this potential confounding factor,we measured the cortical thickness across the whole brain using highresolution T1-weighted magnetic resonance imaging in 145 first-episode and treatment-naive patients with schizophrenia and 147 healthy controls.The results showed that,in the patient group,the frontal,temporal,parietal,and cingulate gyri displayed a significant age-related reduction of cortical thickness.In the control group,age-related cortical thickness reduction was mostly located in the frontal,temporal,and cingulate gyri,albeit to a lesser extent.Importantly,relative to healthy controls,patients exhibited a significantly smaller age-related cortical thickness in the anterior cingulate,inferior temporal,and insular gyri in the right hemisphere.These results provide evidence supporting the existence of neurodegenerative processes in schizophrenia and suggest that these processes already occur in the early stage of the illness.

Testing the role of genetic variation of the MC4R gene in Chinese population in antipsychotic-induced metabolic disturbance

Antipsychotic-induced metabolic disturbance(AIMD) is a common adverse effect of antipsychotics with genetics partly underpinning variation in susceptibility among schizophrenia patients. Melanocortin4 receptor(MC4 R) gene, one of the candidate genes for AIMD, has been under-studied in the Chinese patients. We conducted a pharmacogenetic study in a large cohort of Chinese patients with schizophrenia. In this study, we investigated the genetic variation of MC4 R in Chinese population by genotyping two SNPs(rs489693 and rs17782313) in 1,991 Chinese patients and examined association of these variants with the metabolic effects that were often observed to be related to AIMD. Metabolic measures, including body mass index(BMI), waist circumference(WC), glucose, triglyceride, high-density lipoprotein(HDL), and low-density lipoprotein(LDL) levels were assessed at baseline and after 6-week antipsychotic treatment. We found that interaction of SNP×medication status(drug-na?ve/medicated) was significantly associated with BMI, WC, and HDL change %, respectively. Both SNPs were significantly associated with baseline BMI and WC in the medicated group. Moderate association of rs489693 with WC, Triglyceride, and HDL change % were observed in the whole sample. In the drug-na?ve group, we found recessive effects of rs489693 on BMI gain more than 7%, WC and Triglyceride change %, with AA incurring more metabolic adverse effects. In conclusion, the association between rs489693 and the metabolic measures is ubiquitous but moderate. Rs17782313 is less involved in AIMD. Two SNPs confer risk of AIMD to patients treated with different antipsychotics in a similar way.

Interaction Between Variations in Dopamine D2 and Serotonin 2A Receptor is Associated with Short-Term Response to Antipsychotics in Schizophrenia

Dear Editor,Schizophrenia is a chronic and debilitating brain disorder,which has a strong genetic component with heritability ranging from 66%to 85%[1,2].Currently,antipsychotic drugs remain the most effective treatment for the psychotic symptoms of schizophrenia[3].Because of the severe sideeffects of first-generation antipsychotics(FGAs),secondgeneration antipsychotics(SGAs)have become more widely used in the treatment of schizophrenia.