SYNTHESIS OF NOVEL BI-FUNCTIONAL COPOLYMER BEARING STERICALLY HINDERED PHENOL AND HINDERED AMINE GROUPS VIA RING-OPENING METATHESIS POLYMERIZATION

Norbornene derivatives exo,endo-2-[2-(3,5-di-tert-butyl-4-hydroxyphenoxy)-acetoxy]methyl-5-norbornene(M1) and 3,3,5,5-tetramethyl-4-piperidinyl 5-norbornene-exo,endo-2-carboxylate(M2)were synthesized and polymerized by RuCl_2(=CHPh)(PCy_3)_2 to prepare a novel kind of bi-functional polymer bearing sterically hindered phenol(SHP)and hindered amine(HLAS)groups via ring-opening metathesis polymerization(ROMP).The resulting copolymers were characterized by gel permeation chromatography(GPC),~1H-NMR and differen...

Cyclometalated platinum(Ⅱ) complexes with sterically bulky camphor-derived groups as β-diketonate ancillary ligand:a new route to efficiently reducing π-π interactions and Pt-Pt interactions

A new series of mono-cyclometalated square planar platinum(Ⅱ) complexes have been synthesized and the single-crystal X-ray structures of complex 1 and 2 have been determined.The complexes have the general formula ppyPt(O^O),where ppy is 2-phenylpyridyl,and O^O is β-diketonate ancillary ligands with the acyl substituent group in position 3 of(D)-(+)-camphor.Although,like the many Pt(Ⅱ) complexes with square-planar geometry,these complexes have plane stacking modes in crystal structure,the sterically bulky camphor-derived groups compel extensive slipping of the molecular stacking planes,resulting in the negligible overlapping of the aromatic ring fragments between molecules and the considerable Pt-Pt distance.The resolved spectra and a little shifted emission in solid state of complexes show that there is significant reduction of π-π interactions and Pt-Pt interactions,and suggest these complexes may be good candidates for doped phosphorescent organic light emitting diodes(PhOLEDs) and even for nondoped PhOLEDs.

Understanding Bridging Sites and Accelerating Quantum Efficiency for Photocatalytic CO_(2) Reduction

We report a novel double-shelled nanoboxes photocatalyst architecture with tailored interfaces that accelerate quantum efficiency for photocatalytic CO_(2) reduction reaction(CO_(2)RR)via Mo–S bridging bonds sites in S_(v)–In_(2)S_(3)@2H–MoTe_(2).The X-ray absorption near-edge structure shows that the formation of S_(v)–In_(2)S_(3)@2H–MoTe_(2) adjusts the coordination environment via interface engineering and forms Mo–S polarized sites at the interface.The interfacial dynamics and catalytic behavior are clearly revealed by ultrafast femtosecond transient absorption,time-resolved,and in situ diffuse reflectance–Infrared Fourier transform spectroscopy.A tunable electronic structure through steric interaction of Mo–S bridging bonds induces a 1.7-fold enhancement in S_(v)–In_(2)S_(3)@2H–MoTe_(2)(5)photogenerated carrier concentration relative to pristine S_(v)–In_(2)S_(3).Benefiting from lower carrier transport activation energy,an internal quantum efficiency of 94.01%at 380 nm was used for photocatalytic CO_(2)RR.This study proposes a new strategy to design photocatalyst through bridging sites to adjust the selectivity of photocatalytic CO_(2)RR.

Fine-tuning the activation behaviors of ternary modular cabazitaxel prodrugs for efficient and on-target oral anti-cancer therapy

The disulfide bond plays a crucial role in the design of anti-tumor prodrugs due to its exceptional tumor-specific redox responsiveness. However, premature breaking of disulfide bonds is triggered by small amounts of reducing substances (e.g., ascorbic acid, glutathione, uric acid and tea polyphenols) in the systemic circulation. This may lead to toxicity, particularly in oral prodrugs that require more frequent and high-dose treatments. Fine-tuning the activation kinetics of these prodrugs is a promising prospect for more efficient on-target cancer therapies. In this study, disulfide, steric disulfide, and ester bonds were used to bridge cabazitaxel (CTX) to an intestinal lymph vessel-directed triglyceride (TG) module. Then, synthetic prodrugs were efficiently incorporated into self-nanoemulsifying drug delivery system (corn oil and Maisine CC were used as the oil phase and Cremophor EL as the surfactant). All three prodrugs had excellent gastric stability and intestinal permeability. The oral bioavailability of the disulfide bond-based prodrugs (CTX-(C)S-(C)S-TG and CTX-S-S-TG) was 11.5- and 19.1-fold higher than that of the CTX solution, respectively, demonstrating good oral delivery efficiency. However, the excessive reduction sensitivity of the disulfide bond resulted in lower plasma stability and safety of CTX-S-S-TG than that of CTX-(C)S-(C)S-TG. Moreover, introducing steric hindrance into disulfide bonds could also modulate drug release and cytotoxicity, significantly improving the anti-tumor activity even compared to that of intravenous CTX solution at half dosage while minimizing off-target adverse effects. Our findings provide insights into the design and fine-tuning of different disulfide bond-based linkers, which may help identify oral prodrugs with more potent therapeutic efficacy and safety for cancer therapy.

零维界面的空间位阻效应调控

The regulation mechanism of a zero-dimensional interface towards a catalytic reaction in the setting of a single-atom catalyst has been elusive to researchers.In a recent article published in Journal of the American Chemical Society,Zeng and Zhou et al.differentiated the electronic and steric effects on the oxygen evolution reaction at two distinct zero-dimensional interfaces.

Cold plasma-activated Cu-Co catalysts with CN vacancies for enhancing CO_(2)electroreduction to low-carbon alcohol

Electrocatalytic CO_(2)reduction reaction to low-carbon alcohol is a challenging task,especially high selectivity for ethanol,which is mainly limited by the regulation of reaction intermediates and subsequent C–C coupling.A Cu-Co bimetallic catalyst with CN vacancies is successfully developed by H_(2)cold plasma toward a high-efficiency CO_(2)RR into low-carbon alcohol.The Cu-Co PBA-V_(CN)(Prussian blue analogues with CN vacancies)electrocatalyst yields methanol and ethanol as major products with a total low-carbon alcohol FE of 83.8%(methanol:39.2%,ethanol:44.6%)at-0.9 V vs.RHE,excellent durability(100 h)and a small onset potential of-0.21 V.ATR-SEIRAS(attenuated total internal reflection surface enhanced infrared absorption spectroscopy)and DFT(density functional theory)reveal that the steric hindrance of V_(CN)can enhance the CO generation from*COOH,and the C–C coupling can also be increased by CO spillover on uniformly dispersed Cu atoms.This work provides a strategy for the design and preparation of electrocatalysts for CO_(2)RR into low-carbon alcohol products and highlights the impact of catalyst steric hindrance to catalytic performance.

Arctic Sea Level Variability from Oceanic Reanalysis and Observations

Quantifying the contributions to Arctic sea level(ASL)variability is critical to understand how the Arctic is responsing to ongoing climate change.Here,we use Ocean Reanalysis System 5(ORAS5)reanalysis data and tide gauge and satellite altimetry observations to quantify contributions from different physical processes on the ASL variability.The ORAS5 reanalysis shows that the ASL is rising with a trend of 2.5±0.3 mm yr−1(95%confidence level)over 1979-2018,which can be attributed to four components:(i)the dominant component from the global sea level increase of 1.9±0.5 mm yr−1,explaining 69.7%of the total variance of the ASL time series;(ii)the Arctic Oscillation-induced mass redistribution between the deep central basin and shallow shelves,with no significant trend and explaining 6.3%of the total variance;(iii)the steric sea level increase centering on the Beaufort Gyre region with a trend of 0.5±0.1 mm yr−1 and explaining 29.1%of the total variance of the ASL time series;and(iv)the intrusion of Pacific water into the Arctic Ocean,with no significant trend and contributing 14.2%of the total ASL variability.Furthermore,the dramatic sea ice melting and the larger area of open water changes the impact of the large-scale atmospheric forcing on the ASL variability after 1995,and the ocean dynamic circulation plays a more important role in the ASL variability.

Unraveling abnormal buried interface anion defect passivation mechanisms depending on cation-induced steric hindrance for efficient and stable perovskite solar cells

Although ionic liquids(ILs)have been widely employed to heal the defects in perovskite solar cells(PSCs),the corresponding defect passivation mechanisms are not thoroughly understood up to now.Herein,we first reveal an abnormal buried interface anion defect passivation mechanism depending on cationinduced steric hindrance.The IL molecules containing the same anion([BF4]^(-))and different sizes of imidazolium cations induced by substituent size are used to manipulate buried interface.It was revealed what passivated interfacial defects is mainly anions instead of cations.Theoretical and experimental results demonstrate that the large-sized cations can weaken the ionic bond strength between anions and cations,and facilitate the interaction between anions and SnO2as well as perovskites,which is conducive to interfacial defect passivation and ameliorating interfacial contact.It can be concluded that interfacial chemical interaction strength and defect passivation effect are positively correlated with the size of cations.The discovery breaks conventional thinking that large-sized modification molecules would weaken their chemical interaction with perovskite.Compared with the control device(21.54%),the device based on 1,3-Bis(1-adamantyl)-imidazolium tetrafluoroborate(BAIMBF4)with maximum size cations achieves a significantly enhanced efficiency of 23.61%along with much increased moisture,thermal and light stabilities.

37种脂肪酸甲酯的色谱分离及QSRR研究

采用气相色谱-氢火焰离子化检测器(GC-FID),对常见的37种脂肪酸甲酯在Rtx-wax石英毛细管色谱柱上的分离条件进行了系统的研究,同时采用Steric and Electronic Descriptors(SEDs)表征其分子结构信息,运用多元线性回归(Multiple Linearregression,MLR)建立了脂肪酸甲酯分子结构参数与其气相色谱保留时间的定量结构-色谱保留相关(Quantitative Structure Retention Relationship,QSRR)模型。并采用留一法(Leave-One-Out,LOO)交互检验(Cross-Validation,CV)和外部验证的方法对该模型的稳定性和预测能力进行了评价,其预测值、留一法(Leave-One-Out,LOO)交互检验预测值和外部样本预测值的相关系数R、R CV、Q2ext分别为0.9990、0.9951、0.9995。结果表明,所建模型具有良好的稳定性和预测能力,为脂肪酸的分离、检测及结构表征提供了一条新途径。

Sea-level variation/change and thermal contribution in the Bering Sea

The long-term sea-level trend in the Bering Sea is obtained by the analysisof TOPEX/Poseidon altimeter data, including the data of two tide gauges. The averaged sea-level inthe Bering Sea rises at a rate of 2.47 mm/a from 1992 to 2002. The mean sea-level is falling in themost part of the Bering Sea, especially in its central basin, and it is rising in the northeasternpart of the Bering Sea. During the 1998/99 change, the sea-level anomaly differences exhibit asignificant sea-level anomaly fall in the deep basin of the Bering Sea, which is roughly in the sameposition where a prominent SST fall exists. The maximal fall of sea-level is about 10 cm in thesouthwestern part of the Bering Sea, and the maximal fall of about 2℃ in the SST also appeared inthe same region as the sea level did. The steric sea-level change due to temperature variations isdiscussed. The results are compared with the TOPEX/Poseidon altimeter data at the different spatialscales. It is indicated that the seasonal amplitude of the steric height is about 35% of theobserved TOPEX/Poseidon amplitude, which is much smaller than the 83% in the mid-latitudes area. Thesystematic difference between the TOPEX/Poseidon data with the range of about 7.5 cm and thethermal contribution with the range of about 2.5 cm is about 5 cm. This indicates that the thermaleffect on the sea level is not as important as the case in the mid-latitudes area. In the BeringSea, the phase of the steric height leads the observed sea level by about three months.

Assessing the global averaged sea-level budget from 2003 to 2010

A global mass balance （Greenland and Antarctica ice sheet mass loss, terrestrial water storage） and differ- ent sea-level components （observed sea-level from satellite altimetry, steric sea-level from Ishii data, and ocean mass from gravity recovery and climate experiment, GRACE） are estimated, in terms of seasonal and interannual variabilities from 2003 to 2010. The results show that a detailed analysis of the GRACE time series over the time period 2003-2010 unambiguously reveals an increase in mass loss from the Greenland ice sheet and Antarctica ice sheet. The mass loss of both ice sheets accelerated at a rate of （392.8±70.0） Gt/a during 2003-2010, which contributed （1.09±0.19） mm/a to the global mean sea-level during this time. The net terrestrial water storage （TWS） trend was negative over the 8 a time span, which gave a small positive contribution of （0.25±0.12） mm/a. The interannual variability of the global mean sea-level was at least part- ly caused by year-to-year variability of land water storage. Estimating GRACE-based ice sheet mass balance and terrestrial water storage by using published estimates for melting glaciers, the results further show that the ocean mass increase since 2003 has resulted half from an enhanced contribution of the polar ice sheets, and half from the combined ice sheet and terrestrial water storage loss. Taking also into account the melt- ing of mountain glaciers （0.41 mm/a） and the small GRACE-based contribution from continental waters （0.25 mm/a）, a total ocean mass contribution of （1.75±0.57） mm/a from 2003 to 2010 is found. Such a value represented 75% of the altimetry-based rate of sea-level rise over that period. The contributions to steric sea-level （i.e., ocean thermal expansion plus salinity effects） are estimated from： （1） the difference between altimetry-based sea-level and ocean mass change and （2） the latest Ishii data. The inferred steric sea-level rate from （1） （1.41 mm/a from 2003 to 2010） did not agree well with the Ishii-based value also estimated here （0.44 mm/a from 2003 to 2010）, but phase. The cause for such a discrepancy is not yet known but may be related to inadequate sampling of in situ ocean temperature and salinity measurements.

THE STEPWISE EXCHANGE ACTION AND STERIC HINDRANCE EFFECT OF ORGANIC PHENOLS ON CLAYS IN SEAWATER

The exchange action of six types of organic phenols on clay surfaces in seawater is systematically studied in this work. The following significant conclusions are drawn from the experiments. (1) The interaction of organic phenols with montmorillonite, illite and kaolinite in seawater is monovalent anion exchage.(2) Their isotherms of stepwise exchage on clay surfaces belong to the Langmuir type or stepwise type.(3) The discovery of the"steric hindrance effects of stepwise exchange of organic phenols on clays surfaces", and revelation of an exchange mechanisrn diffeient from that in references are the greatest achieverments in this work.

Sea level rise projection in the South China Sea from CMIP5 models

Future potential sea level change in the South China Sea （SCS） is estimated by using 24 CMIP5 models under different representative concentration pathway （RCP） scenarios. By the end of the 21st century （2081–2100 relative to 1986–2005）, the multimodel ensemble mean dynamic sea level （DSL） is projected to rise 0.9, 1.6, and 1.1 cm under RCP2.6, RCP4.5, and RCP8.5 scenarios, respectively, resulting in a total sea level rise （SLR） of 40.9, 48.6, and 64.1 cm in the SCS. It indicates that the SCS will experience a substantial SLR over the 21st century, and the rise is only marginal larger than the global mean SLR. During the same period, the steric sea level （SSL） rise is estimated to be 6.7, 10.0, and 15.3 cm under the three scenarios, respectively, which accounts only for 16%, 21% and 24% of the total SLR in this region. The changes of the SSL in the SCS are almost out of phase with those of the DSL for the three scenarios. The central deep basin has a slightly weak DSL rise, but a strong SSL rise during the 21st century, compared with the north and southwest shelves.

Kinetics of protein adsorption/desorption mediated by pH-responsive polymer layer

We propose a new way of regulating protein adsorption by using a pH-responsive polymer. According to the the- oretical results obtained from the molecular theory and kinetic approaches, both thermodynamics and kinetics of protein adsorption are verified to be well controlled by the solution pH. The kinetics and the amount of adsorbed proteins at equi- librium are greatly increased when the solution environment changes from acid to neutral. The reason is that the increased pH promotes the dissociation of the weak polyelectrolyte, resulting in more charged monomers and more stretched chains. Thus the steric repulsion within the polymer layer is weakened, which effectively lowers the barrier felt by the protein during the process of adsorption. Interestingly, we also find that the kinetics of protein desorption is almost unchanged with the variation of pH. It is because although the barrier formed by the polymer layer changes along with the change of pH, the potential at contact with the surface varies equally. Our results may provide useful insights into controllable protein adsorption/desorption in practical applications.

Dispersion of Co-poly Carboxylate Superplasticizer Containing Poiyether Side Chain

Free radical co-polymerization was employed to synthesize co-poly carboxylate (PC) superplasticizers with different amount of carboxyl and methyl polyethylene glycol (MPEG) side chain.Dispersion ability and retention of PC were compared with one another. The results show that increase of side chain is advantageous to dispersion, but it decreases when amount of MPEG is beyond a certain value which is different with the proportion of carboxyl. If the amount of carboxyl increases, the influence of side chain in copolymer on dispersion diminishes. Polyether side chain is advantageous to retention. And the author explained the mechanism of PC using the theory of steric repulsive force.

Sea level change under IPCC-A2 scenario in Bohai, Yellow, and East China Seas

Because of the environmental and socioeconomic impacts of anthropogenic sea level rise （SLR）, it is very important to understand the processes leading to past and present SLRs towards more reliable future SLR projections. A regional ocean general circulation model （ROGCM）, with a grid refinement in the Bohai, Yellow, and East China Seas （BYECSs）, was set up to project SLR induced by the ocean dynamic change in the 21st century. The model does not consider the contributions from ice sheets and glacier melting. Data of all forcing terms required in the model came from the simulation of the Community Climate System Model version 3.0 （CCSM3） under the International Panel on Climate Change （IPCC）-A2 scenario. Simulation results show that at the end of the 21st century, the sea level in the BYECSs will rise about 0.12 to 0.20 m. The SLR in the BYECSs during the 21st century is mainly caused by the ocean mass redistribution due to the ocean dynamic change of the Pacific Ocean, which means that water in the Pacific Ocean tends to move to the continental shelves of the BYECSs, although the local steric sea level change is another factor.

Study of Complexes of Lanthanum with Amino Acids by Titration Calorimeter

The stability constants and thermodynamic functions for complexes of lanthanum with eight kind of amino acids according to 1∶1 and 1∶2 in proportion have been determined by titration calorimeter at 298.15 K. The enthalpy change makes a predominant contribution to the stability of these complexes. The ring in amino acid associated with lanthanum ion helps to enhance the stability of complexes. Steric effects between rings in complexes leads to that the equilibrium constants of reaction of the complexes (1∶2) is much less than that of the complexes (1∶1).

The water mass variability and southward shift of the Southern Hemisphere mid-depth supergyre

The Southern Hemisphere subtropical supergyre at intermediate depths connects all three ocean basins and plays a significant role in responding and conveying the climate-change-related variations in the glob- al ocean. On the basis of the Simple Ocean Data Assimilation/SODA） ocean reanalysis, the thermohaline variability and southward shift of the mid-depth supergyre are demonstrated. The steric height of the sub- surface relative to 1 500 m （400-1 500 m） from the SODA depicts exactly the flow patterns and variability of the oceanic supergyre. During 1958-2007 the water masses in the gyre interiors become cooler/fresher, with the significant exceptions of the Agulhas Current system and Agulhas leakage. The results also exhibit a pronounced strengthening of the inter-basin connection of the supergyre, and the strongest southward shift, by about 2.5° over the whole period, occurs in the central-south Pacific, which is associated with the changes in the basin-scale wind forcing.

Comparing the steric height in the Nordic Seas with satellite altimeter sea surface height

In this study the steric height anomaly which is calculated from the hydrological data （EN3） is compared with the sea level anomaly derived from satellite altimetry in the Nordic Seas. The overall pattern of steric height is that it is higher in the margin area and lower in the middle area. The extreme values of steric height linear change from 1993 to 2010 occur in the Lofoten Basin and off the Norwegian coast, respectively. Such a distribution may be partly attributed to the freshening trend of the Nordic Seas. The correlation between SLA （sea level anomaly） and SHA （steric height anomaly） is not uniform over the Nordic Seas. The time series of SLA and SHA agree well in the Lofoten Basin and northern Norwegian Basin, and worse in the northern Norwegian Sea, implying that the baroclinic effect plays a dominant role in most areas in the Norwegian Sea and the barotropic effect plays a dominant role in the northern Norwegian Sea. The weaker correlations between SLA and SHA in the Greenland and Iceland Seas lead a conclusion that the barotropic contribution is significant in these areas. The area-mean SHA over the entire Nordic Seas has similar amplitudes compared with the SLA during 1996-2002, but SHA has become lower than SLA, being less than half of SLA since 2006.

Steric Sea Level Change in Twentieth Century Historical Climate Simulation and IPCC-RCP8.5 Scenario Projection: A Comparison of Two Versions of FGOALS Model

To reveal the steric sea level change in 20th century historical climate simulations and future climate change projections under the IPCC＇s Representative Concentration Pathway 8.5 （RCP8.5） scenario, the results of two versions of LASG/IAP＇s Flexible Global Ocean-Atmosphere-Land System model （FGOALS） are analyzed. Both models reasonably reproduce the mean dynamic sea level features, with a spatial pattern correlation coefficient of 0.97 with the observation. Characteristics of steric sea level changes in the 20th century historical climate simulations and RCPS.5 scenario projections are investigated. The results show that, in the 20th century, negative trends covered most parts of the global ocean. Under the RCPS.5 scenario, global-averaged steric sea level exhibits a pronounced rising trend throughout the 21st century and the general rising trend appears in most parts of the global ocean. The magnitude of the changes in the 21st century is much larger than that in the 20th century. By the year 2100, the global-averaged steric sea level anomaly is 18 cm and 10 cm relative to the year 1850 in the second spectral version of FGOALS （FGOALS-s2） and the second grid-point version of FGOALS （FGOALS-g2）, respectively. The separate contribution of the thermosteric and halosteric components from various ocean layers is further evaluated. In the 20th century, the steric sea level changes in FGOALS-s2 （FGOALS-g2） are largely attributed to the thermosteric （halosteric） component relative to the pre-industrial control run. In contrast, in the 21st century, the thermosteric component, mainly from the upper 1000 m, dominates the steric sea level change in both models under the RCPS.5 scenario. In addition, the steric sea level change in the marginal sea of China is attributed to the thermosteric component.