近红外光谱法在红曲菌固态发酵过程参数检测中的应用

研究了近红外光谱技术快速检测红曲菌固态发酵过程参数水分含量和pH值的可行性。针对传统基于间隔策略波长选择方法忽略非线性因素的缺点,采用一种基于最小二乘支持向量机(Least squares support vector machines,LS-SVM)非线性模型的波长筛选算法：联合区间最小二乘支持向量机(Synergy interval least squares support vector machines,siLS-SVM),并将新算法与相关系数法、iPLS算法、siPLS算法对比。实验结果显示,联合siLS-SVM算法和LS-SVM模型取得了最好的预测效果,水分含量、pH值的预测集相关系数(Rp)分别为0.962 1、0.976 1,预测均方根误差(RMSEP)分别为0.012 9、0.145 2,表明模型具有较好的拟合度和预测性能。应用近红外光谱法进行红曲菌固态发酵过程的水分含量和pH值的快速检测可行,该方法为进一步实现其过程参数的在线检测及发酵条件优化提供了技术基础。     

A 3-fold Interpenetrated lvt Cd(Ⅱ) Network Constructed from 4-[(3-pyridyl)methylamino]benzoate Acid

A new three-dimensional(3D) coordination polymer, [Cd(L)2H2O]n·5nH2O 1 with 4-[(3-pyridyl)methylamino]benzoate acid(HL), has been synthesized by slow evaporation solvent at room temperature, and structurally characterized by elemental analysis, IR spectrum, thermal analysis, fluorescence spectrum and single-crystal X-ray diffraction. Compound 1 crystallizes in the tetragonal system, space group I-4, with a = 20.7937(16), c = 13.515(2), V = 5843.5(11) 3, C26H34CdN4O10, Mr = 674.97, Dc = 1.534 g/cm3, μ(MoKα) = 0.808 mm-1, F(000) = 2768, Z = 8, the final R = 0.0276 and wR = 0.0691 for 5323 observed reflections(I 2σ(I)). The result of thermal analysis shows that 1 is stable under 290 ℃. Moreover, it exhibits blue photoluminescence at room temperature.     

Rheo-optical near-infrared (NIR) spectroscopy study of low-density polyethylene (LDPE) in conjunction with projection two-dimensional (2D) correlation analysis

A rheo-optical characterization technique based on near-infrared (NIR) spectroscopy is developed specifically to probe the submolecular-level deformation caused during a mechanical test. An illustrative example of the mechanical deformation of low-density polyethylene (LDPE) is provided to show how it can be utilized. A set of NIR spectra of the polymer sample were collected by using an acousto-optic tunable filter (AOTF) NIR spectrometer coupled with a tensile testing machine as an excitation device. While the substantial level of variation of spectral intensity was readily captured during the mechanical deformation of the LDPE, main feature of the NIR spectra was overwhelmed by the contribution from the baseline change. Projection 2D correlation analysis was then applied to selectively extract the signal contribution from the baseline fluctuation. The 2D correlation spectra revealed the predominant extension of amorphous tie chains followed by the rotation of crystalline lamellae, which induce elastic and plastic deformation of the LDPE, respectively.     

含噻吩杂环Schiff碱及其配合物的合成与发光性质

在热乙醇中合成了2-乙酰基噻吩缩异烟酰肼及其与Cd(II)、Cu(II)和Zn(II)形成的三种配合物;利用元素分析、摩尔电导测定,以及红外光谱、紫外光谱和热分析确定了合成产物的组成和结构,并测定了配合物的组成及发光性质.结果表明,酰肼的配位方式的不同导致配合物呈现不同的发光性质.     

基于双极性铼配合物的低浓度淬灭电致发光器件

合成了一种含双极性9,9-双(9-乙基咔唑-3-基)-4,5-二氮芴(ECAF)配体的新型三羰基铼配合物Re(CO)3(ECAF)Cl,通过核磁共振氢谱及高分辨质谱对其结构进行了确定。以含有4,5-二氮-9,9-螺二芴(SB)配体的铼配合物Re(CO)3(SB)Cl作为参比物,对比研究了其热稳定性及光电性能。结果表明,与参比物的分解温度(366℃)相比,配合物Re(CO)3(ECAF)Cl有极好的热稳定性(热分解温度419℃)。由于富电子咔唑基团导致的能隙增大,相比参比物的发光波长(572 nm),Re(CO)3(ECAF)Cl的发光波长蓝移至565 nm。Re(CO)3(ECAF)Cl的发光量子效率(39%)稍高于参比物(37%)。以旋涂法制成电致发光器件后,基于Re(CO)3(ECAF)Cl器件的最佳掺杂浓度(质量分数)高达30%,是基于参比物器件的2.4倍,而且开启电压低至2.9 V,明显比参比物器件的4.0 V低,说明ECAF配体能有效抑制发光浓度淬灭,且明显改善了铼配合物的载流子传输性能。基于Re(CO)3(ECAF)Cl器件的最大电流效率及最大外量子效率分别为8.2 cd·A^-1和3.0%,低于参比物器件的9.7 cd·A^-1和3.9%。     

3,5-二(2',5'-苯二羧酸)苯甲酸构筑的金属有机配合物的荧光识别及磁性

设计合成了3种新颖的金属有机配合物（MOCs）：{[Pb₂（HL）（phen）]·2H₂O}_n（1）,{[Ni（H₃L）（4,4''-bipy）_1.5（H₂O）₄]·6H₂O}_n（2）和{[Ni₂（HL）（1,4-bibb）（H₂O）]·（CH₃CN）·H₂O}_n（3）（H₅L=3,5-二（2'',5''-苯二羧酸）苯甲酸,phen=1,10-菲咯啉,4,4''-bipy=4,4''-联吡啶,1,4-bibb=1,4-二（苯并咪唑）苯）,并通过单晶X射线衍射、红外光谱（IR）、热重分析（TG）和粉末衍射对它们进行结构表征。结构分析表明1是基于[Pb₂（μ₂-COO）₂（μ₁-COO）₄]SBUs的一维链状结构;2是二维层状结构,其拓扑符号为{4.6²}₂{4².6².8²};3是一个3D网络结构,其拓扑符号为{6².8⁴}{6⁴.8²}₂。进一步研究了配合物荧光和磁性能。荧光检测显示,配合物1在水溶液中可以高灵敏识别Fe³⁺和Cr₂O₇^2-离子。同时研究了配合物1对Fe³⁺和Cr₂O₇^2-猝灭机理。磁性分析表明配合物3中的Ni（Ⅱ）离子之间存在反铁磁相互作用。     

Effective Utilization of NIR Wavelengths for Photo‐Controlled Polymerization: Penetration Through Thick Barriers and Parallel Solar Syntheses

This contribution details an efficient and controlled photopolymerization regulated by far‐red (λ=680 nm) and NIR (λ=780 and 850 nm) light in the presence of aluminium phthalocyanine and aluminium naphthalocyanine. Initiating radicals are generated by photosensitization of peroxides affording an effective strategy that provides controlled polymerization of a variety of monomers with excellent living characteristics. Critically, long wavelength irradiation provides penetration through thick barriers, affording unprecedented rates of controlled polymerization that can open new and exciting applications. Furthermore, a more optimized approach to performing solar syntheses is presented. By combining the narrow Q‐bands of these photocatalysts with others possessing complementary absorptions, layered, independent polymerizations and organic transformations may be performed in parallel under a single broadband emission source, such as sunlight.     

Unraveling the Impact of Gold(I)–Thiolate Motifs on the Aggregation‐Induced Emission of Gold Nanoclusters

Aggregation‐induced emission (AIE) provides an efficient strategy to synthesize highly luminescent metal nanoclusters (NCs), however, rational control of emission energy and intensity of metal NCs is still challenging. This communication reveals the impact of surface Au^I‐thiolate motifs on the AIE properties of Au NCs, by employing a series of water‐soluble glutathione (GSH)‐coordinated Au complexes and NCs as a model ([Au₁₀SR₁₀], [Au₁₅SR₁₃], [Au₁₈SR₁₄], and [Au₂₅SR₁₈]^?, SR=thiolate ligand). Spectroscopic investigations show that the emission wavelength of Au NCs is adjustable from visible to the near‐infrared II (NIR‐II) region by controlling the length of the Au^I‐SR motifs on the NC surface. Decreasing the length of Au^I‐SR motifs also changes the origin of cluster luminescence from AIE‐type phosphorescence to Au⁰‐core‐dictated fluorescence. This effect becomes more prominent when the degree of aggregation of Au NCs increases in solution.     

Real‐Time In Vivo Detection of Cellular Senescence through the Controlled Release of the NIR Fluorescent Dye Nile Blue

In vivo detection of cellular senescence is accomplished by using mesoporous silica nanoparticles loaded with the NIR‐FDA approved Nile blue (NB) dye and capped with a galactohexasaccharide ( S3 ). NB emission at 672 nm is highly quenched inside S3 , yet a remarkable emission enhancement is observed upon cap hydrolysis in the presence of β‐galactosidase and dye release. The efficacy of the probe to detect cellular senescence is tested in vitro in melanoma SK‐Mel‐103 and breast cancer 4T1 cells and in vivo in palbociclib‐treated BALB/cByJ mice bearing breast cancer tumor.