炔醇选择加氢催化剂研究进展

炔醇选择加氢制备相应的烯醇在医药、农药、食品添加剂、香精、香料和聚合物单体等众多高端精细化学品合成中是一个非常重要的化工过程.通过一系列复杂的平行和连续的反应,炔醇可加氢生产若干个关键中间体.提高对烯醇的选择性和保持催化剂的效率是工业生产的关键,也是一个巨大的挑战.迄今为止,各种有效的贵金属和非贵金属催化剂得到了广泛的发展,尤其是钯基和镍基多相催化剂取得了显著进展.从经典的Lindlar催化剂和Raney-Ni催化剂到生物基金属催化新材料,本文系统综述了近几十年炔醇选择加氢催化剂的设计,从催化剂本身的金属活性中心、助剂(第二金属、有机配体和稳定剂)的作用、载体的性质(孔结构、酸碱性、金属与载体强相互作用)以及反应条件等因素对催化活性、目标产物的选择性和稳定性的影响进行了系统的综述.借助先进的表征技术、理论计算和实验研究,本文还阐述了炔醇选择加氢反应的机理.研究发现:(1)在所有贵金属催化剂中,Pd基催化剂对炔醇半加氢制烯醇的效率最高,且选择性最好.稳定剂和抑制剂的加入可以提高中间体的选择性,但在一定程度上降低了催化活性.此外,Zn,In和Cu等第二金属的掺杂可以调节金属Pd的几何效应和电子结构,从而调节底物和中间产物的吸附,并抑制过度加氢.与传统的Lindlar型催化剂相比,这种Pd基合金或金属间化合物可广泛应用于炔醇的选择性加氢反应,显著提高烯醇的选择性,且不需要引入有毒添加剂.(2)Ni基材料作为可替代贵金属催化剂,可分别实现炔醇的高选择性加氢制备烯醇或烷醇.然而,与贵金属催化剂相比,其反应条件相对苛刻.炔醇加氢产物分布很大程度上取决于助剂的引入和载体的酸性.此外,碳物种易沉积在Ni表面造成活性位点被覆盖,且在水热环境下Ni颗粒因团聚而失活,因此,用于炔醇选择加氢反应的镍基催化剂稳定性仍有待提高.尽管炔醇选择加氢反应在学术界和工业界都有广泛研究,但对于这些催化体系,特别是催化剂的结构性能关系和反应机理,仍有待进一步明确.(1)原位表征技术和理论计算的发展,将有助于人们理解炔醇选择性加氢的催化过程,并指导研究者根据炔醇加氢的特点设计出具有良好选择性的高效催化剂.(2)烯醇类产品一般应用于医药中间体和高分子单体,对产品纯度要求较高.因此,在不引入有毒添加剂的情况下,设计高效、高选择性催化剂至关重要.(3)水相或醇相中炔醇选择加氢反应对催化剂的水热稳定性有很高的要求.通过锚定和包覆来增强金属与载体的相互作用,抑制金属纳米粒子的聚集和流失是一种有效的手段.此外,在炔醇选择加氢反应中引入耐水载体可以有效提高催化剂的稳定性.(4)短碳链炔醇催化选择加氢反应一直是研究的热点.然而,关于长碳链炔醇的选择加氢反应过程,国内外报道相对较少.基于长碳链炔醇底物分子的空间位阻效应,有必要设计具有特殊孔道结构的选择加氢催化剂.(5)目前,绝大多数炔醇选择加氢过程还处于间歇性操作.随着市场对烯醇的需求不断增加,为了获得高品质的产品,连续化操作将是一个必然趋势.

Successful Production of an All-Female Common Carp (Cyprinus carpio L.) Population Using cyp17a1-Deficient Neomale Carp

Due to sexual dimorphism in the growth of certain cultured fish species,the production of monosex fishes is desirable for the aquaculture industry.Nowadays,the most widely practiced technique available for the mass production of monosex fish populations is sex steroid-induced sex reversal.Here,a novel strategy for the successful production of all-female(AF)common carp(Cyprinus carpio L.),to take advantage of the sexual dimorphism in growth documented in this species,has been developed using genetic engineering via single gene-targeting manipulation without any exogenous hormone treatments.Male and female heterozygous cyp17a1-deficient common carp were first obtained using the clustered regularly interspaced short palindromic repeats/CRISPR-associated endonuclease 9(CRISPR/Cas9)technique.An all-male phenotype for homozygous cyp17a1-deficient carp,regardless of the individuals’sexdetermination genotypes(XY or XX),has been observed.A male-specific DNA marker newly identified in our laboratory was used to screen the neomale carp population with the XX genotype from the cyp17a1-deficient carp.These neomale carp develop a normal testis structure with normal spermatogenesis and sperm capacity.The neomale common carp were then mated with wild-type(WT)females(cyp17a1^(+/+)XX genotype)using artificial fertilization.All the AF offspring sample fish from the neomale-WT female mating were confirmed as having the cyp17a^(1+/-)XX genotype,and normal development of gonads to ovaries was observed in 100.00%of this group at eight months post-fertilization(mpf).A total of 1000 carp fingerlings,500 from the WT male and female and 500 from the neomale and WT female mating,were mixed and reared in the same pond.The average body weight of cyp17a1^(+/-)XX females was higher by 6.60%(8 mpf)and 32.66%(12 mpf)than that of the control common carp.Our study demonstrates the first successful production of a monosex teleost population with the advantages of sexual dimorphism in growth using genetic manipulation targeting a single locus.

Recent Advances in Space-Deployable Structures in China

Deployable space structure technology is an approach used in building spacecraft,especially when realizing deployment and folding functions.Once in orbit,the structures are released from the fairing,deployed,and positioned.With the development of communication,remote-sensing,and navigation satellites,space-deployable structures have become cutting-edge research topics in space science and technology.This paper summarizes the current research status and development trend of spacedeployable structures in China,including large space mesh antennas,space solar arrays,and deployable structures and mechanisms for deep-space exploration.Critical technologies of space-deployable structures are addressed from the perspectives of deployable mechanisms,cable-membrane form-finding,dynamic analysis,reliable environmental adaptability analysis,and validation.Finally,future technology developments and trends are elucidated in the fields of mesh antennas,solar arrays,deployable mechanisms,and on-orbit adjustment,assembly,and construction.

RAIM Algorithm Based on Fuzzy Clustering Analysis

With the development of various navigation systems(such as GLONASS,Galileo,BDS),there is a sharp increase in the number of visible satellites.Accordingly,the probability of multiply gross measurements will increase.However,the conventional RAIM methods are difficult to meet the demands of the navigation system.In order to solve the problem of checking and identify multiple gross errors of receiver autonomous integrity monitoring(RAIM),this paper designed full matrix of single point positioning by QR decomposition,and proposed a new RAIM algorithm based on fuzzy clustering analysis with fuzzy c-means(FCM).And on the condition of single or two gross errors,the performance of hard or fuzzy clustering analysis were compared.As the results of the experiments,the fuzzy clustering method based on FCM principle could detect multiple gross error effectively,also achieved the quality control of single point positioning and ensured better reliability results.

GSTAR:an innovative software platform for processing space geodetic data at the observation level

To meet the demands for the data combination with multiple space geodetic techniques at the observation level,we developed a new software platform with high extensibility and computation efficiency,named space Geodetic SpatioTemporal data Analysis and Research software(GSTAR).Most of the modules in the GSTAR are coded in C++with object-oriented programming.The layered modular theory is adopted for the design of the software,and the antenna-based data architecture is proposed for users to construct personalized geodetic application scenarios easily.The initial performance of the GSTAR software is evaluated by processing the Global Navigation Satellite System(GNSS)data collected from 315 globally distributed stations over two and a half years.The accuracy of GNSS-based geodetic products is evaluated by comparing them with those released by International GNSS Service(IGS)Analysis Centers(AC).Taking the products released by European Space Agency(ESA)as reference,the Three-Dimension(3D)Root-Mean-Squares(RMS)of the orbit differences are 2.7/6.7/3.3/7.7/21.0 cm and the STandard Deviations(STD)of the clock differences are 19/48/16/32/25 ps for Global Positioning System(GPS),GLObal NAvigation Satellite System(GLONASS),Galileo navigation satellite system(Galileo),BeiDou Navigation Satellite System(BDS),Medium Earth Orbit(MEO),and BDS Inclined Geo-Synchronous Orbit(IGSO)satellites,respectively.The mean values of the X and Y components of the polar coordinate and the Length of Day(LOD)with respect to the International Earth Rotation and Reference Systems Service(IERS)14 C04 products are-17.6 microarc-second(μas),9.2μas,and 14.0μs/d.Compared to the IGS daily solution,the RMSs of the site position differences in the north/east/up direction are 1.6/1.5/3.9,3.8/2.4/7.6,2.5/2.4/7.9 and 2.7/2.3/7.4 mm for GPS-only,GLONASS-only,Galileo-only,and BDS-only solution,respectively.The RMSs of the differences of the tropospheric Zenith Path Delay(ZPD),the north gradients,and the east gradients are 5.8,0.9,and 0.9 mm with respect to the IGS products.The X and Y components of the geocenter motion estimated from GPS-only,Galileo-only,and BDS-only observations well agree with IGS products,while the Z component values are much nosier where anomalous harmonics in GNSS draconitic year can be found.The accuracies of the above products calculated by the GSTAR are comparable with those from different IGS ACs.Compared to the precise scientific orbit products,the 3D RMS of the orbit differences for the two Gravity Recovery and Climate Experiment Follow-on(GRACE-FO)satellites is below 1.5 cm by conducting Precise Point Positioning with Ambiguity Resolution(PPP-AR).In addition,a series of rapid data processing algorithms are developed,and the operation speed of the GSTAR software is 5.6 times faster than that of the Positioning and Navigation Data Analyst(PANDA)software for the quad-system precise orbit determination procedure.

Correlation-weighted least squares residual algorithm for RAIM

The Least Squares Residual(LSR)algorithm,one of the classical Receiver Autonomous Integrity Monitoring(RAIM)algorithms for Global Navigation Satellite System(GNSS),presents a high Missed Detection Risk(MDR)for a large-slope faulty satellite and a high False Alarm Risk(FAR)for a small-slope faulty satellite.From the theoretical analysis of the high MDR and FAR cause,the optimal slope is determined,and thereby the optimal test statistic for fault detection is conceived,which can minimize the FAR with the MDR not exceeding its allowable value.To construct a test statistic approximate to the optimal one,the CorrelationWeighted LSR(CW-LSR)algorithm is proposed.The CW-LSR test statistic remains the sum of pseudorange residual squares,but the square for the most potentially faulty satellite,judged by correlation analysis between the pseudorange residual and observation error,is weighted with an optimal-slope-based factor.It does not obey the same distribution but has the same noncentral parameter with the optimal test statistic.The superior performance of the CW-LSR algorithm is verified via simulation,both reducing the FAR for a small-slope faulty satellite with the MDR not exceeding its allowable value and reducing the MDR for a large-slope faulty satellite at the expense of FAR addition.

Hyperandrogenism in POMCa-deficient zebrafish enhances somatic growth without increasing adiposity

The endocrine regulatory roles of the hypothalamic-pituitary-adrenocortical axis on anxiety-like behavior and metabolic status have been found throughout animal taxa.However,the precise effects of the balancing adrenal corticosteroid biosynthesis under the influence of adrenocorticotrophic hormone(ACTH),a pro-opiomelanocortin(POMC)-derived peptide,on animal energy expenditure and somatic growth remain unknown.POMC has also been identified as one of the candidate loci for polycystic ovary syndrome,which features hyperandrogenism and some prevalence of obesity in patients.Here we show that zebrafish lacking functional POMCa exhibit similar phenotypes of stress response and body weight gain but not obesity as observed in mammalian models.In contrast with the impaired anorexigenic signaling cascade of melanocyte-stimulating hormones and leptin,which are responsible for their obesity-prone weight gain observed in various pome mutant mammals,analyses with our pomca mutant series indicate that ACTH is the key regulator for the phenotype with enhanced somatic growth without obesity in pomca-deficient zebrafish.Hypocortisolism associated with hyperandrogenism has been observed in the pomca-deficient zebrafish,with enhanced activation of mammalian target of rapamycin complex 1;reutilization of amino acids and fatty acid^-oxidation are observed in the muscle tissue of the pomca-deficient fish.After reducing hyperandrogenism by crossing our pomca mutant fish with a cy p l 7a 1-deficient background,the phenotype of enhanced somatic growth in pomca-deficient fish was no longer observed.Thus,our work also demonstrated that the role of POMCa in stress response seems to be conserved in vertebrates,whereas its effect on adipostasis is unique to teleosts.

Genomic polymorphisms at the crhr2 locus improve feed conversion efficiency through alleviation of hypothalamus-pituitary-interrenal axis activity in gibel carp(Carassius gibelio)

Improvement in fish feed conversion efficiency(FCE)is beneficial for sustaining global food fish supplies.Here,we show that a set of polymorphisms at locus of the corticotropin releasing hormone receptor 2(crhr2),which is involved in hypothalamuspituitary-interrenal(HPI)axis signaling,is associated with improved FCE in farmed allogynogenetic gibel carp strain CAS Ⅲ compared with that in the wild gibel carp strain Dongting(DT).This set of polymorphisms downregulates the expression levels of crhr2 mRNA in the brain and pituitary tissues in gibel carp strain CAS Ⅲ compared with those in strain DT.Furthermore,compromised HPI axis signaling is observed in gibel carp strain CAS Ⅲ,such as decreased α-melanocyte stimulating hormone protein levels,plasma cortisol content,and stress responses.Moreover,enhanced activation of protein kinase B/mammalian target of rapamycin complex 1 signaling observed in the muscle tissue of strain CAS Ⅲ in comparison to that in strain DT indicated elevated anabolic metabolism in strain CAS Ⅲ.Thus,these studies demonstrate that the genetic markers associated with compromised HPI axis signaling,such as crhr2,are potentially useful for genetic selection toward improvement in farmed fish growth and FCE,which would reduce fishmeal consumption and thereby indirectly facilitate sustainable fisheries.

Near real-time modeling of global ionospheric vertical total electron content using hourly IGS data

The International GNSS Service(IGS) has been providing reliable Global Ionospheric Maps(GIMs) since 1998. The Ionosphere Associate Analysis Centers(IAACs) model the global ionospheric Total Electron Content(TEC) and generate the daily GIM products within the context of the IGS. However, the rapid and final daily GIM products have a latency of at least one day and one week or so, respectively. This limits the value of GIM products in real-time GNSS applications.We propose and develop an approach for near real-time modeling of global ionospheric TEC by using the hourly IGS data. We perform an experiment in a real operating environment to generate near real-time GIM(named BUHG) products for more than two years. Final daily GIM products,Precise Point Positioning(PPP) based VTEC resources, and JASON-3 Vertical TEC(VTEC) measurements are collected for testing the performance of BUHG. The results show that the performance of BUHG is very close to that of the daily GIM products. Also, there is good agreement between BUHG and PPP-derived VTEC as well as with JASON-3 VTEC. It is possible that BUHG would be further improved with an increase in available hourly GNSS data.