FTIR spectroscopic investigation of thermal effects in semi‐syndiotactic polypropylene

The temperature‐dependent behavior of individual components within metallocene‐catalyzed semisyndiotactic polypropylenes (semi‐sPP) with a wide range of stereoregular content (26 to 96% rr) is studied using Fourier transform infrared (FTIR) spectroscopy and temperature‐modulated differential scanning calorimetry (DSC). Changes in sensitive, high‐resolution absorbance spectra are observed as melt‐slow‐cooled thin films are subjected to stepwise temperature increases. In general, spectral bands previously identified as being sensitive to ordered structures (e.g., conformed chains, crystal morphs) appear to follow overall trends of shifting to lower wavenumbers (energies), broadening, and decreasing in peak area intensity as temperature increases. Peaks that appear due to “splitting” (observed in more stereoregular materials) show a trend toward coalescence as temperature increases; this corresponds to a gradual loss of chain conformational order. Gauche‐gauche‐trans‐trans (ggtt)_n helical and all‐trans (tttt)_n planar zigzag‐conformed chains that participate in the crystalline‐amorphous interfacial region (“mesophase”) appear to be more stable (i.e., they do not lose their conformational order as easily) with increasing temperature in materials with a greater degree of syndiotacticity. Moreover, IR data correspond well with modulated DSC endotherms located near 50 °C and 70 °C. At each transition temperature—thought to represent, respectively, a thermally driven chain conformation from planar zigzags to helices, and a dynamic disorder of helices marked by rapid gauche ? trans isomerization—the IR absorbance ratio, A₉₇₈/A₉₆₃, which represents the relative population of helical chains, undergoes an accelerated decrease. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 439–461, 2005     

近红外光谱法同时测定鱼粉中脂肪,蛋白质和水份

本文使用近红外光谱分析法同时测定鱼粉中的蛋白质，脂肪和水份。本法简便，无污染。     

meso‐Dibenzoporphycene has a Large Bathochromic Shift and a Porphycene Framework with an Unusual cis Tautomeric Form

meso‐Monobenzoporphycene (mMBPc) and meso‐dibenzoporphycene (mDBPc), in which one or two benzene moieties are fused at ethylene‐bridged positions (meso‐positions) of porphycene, were prepared in an effort to further delocalize the π‐electrons within the porphycene molecule. mMBPc and mDBPc were fully characterized by mass spectrometry, ¹H and ¹³C NMR spectroscopy, and X‐ray crystallography. The longest‐wavelength Q‐bands of mMBPc and mDBPc are red‐shifted by 92 nm and 418 nm, respectively, compared to that of the unsubstituted porphycene (Pc). Electrochemical measurements indicate that the HOMO is destabilized and the LUMO is stabilized by the fused benzene moieties at the meso positions. Furthermore, both XPS and theoretical studies support the presence of a cis tautomeric form in the ground state of mDBPc, despite the fact that essentially all known porphycene derivatives adopt the trans tautomeric form.     

Observation of the multiple halogenation of peptides in the electrospray ionization source

The chlorination of peptides and proteins is an important posttranslational modification, which is a physiological signature of an enzyme myeloperoxidase and can serve as a potential biomarker of some diseases (Parkinson's disease, Alzheimer's disease, etc.). The quantification of the chlorinated peptides has been very challenging in part due to their low levels and artifacts associated with sample preparation. One of the most convenient and promising methods to detect and investigate the chlorinated peptides in the biological samples is the electrospray ionization (ESI) mass spectrometry coupled to the fragmentation techniques (collision‐induced dissociation and electron capture dissociation/electron transfer dissociation). We have shown that if the chlorine anions are present in the solution, then the peptide can undergo the chlorination during the ESI ionization. The effect was found to depend on the values of electric potentials of metal parts of the ESI interface. It was found that the grounding of ESI syringe results in the formation of an additional electric loop leading to the electrolytic production of Cl₂ and as a consequence the hypochlorous acid inside the ESI needle. Hypochlorous acid reacts with amino groups of peptides and proteins producing chloramine or causing the protein cleavage. In the paper, it is shown on the example of the solution of the several peptides in the presence of HCl that by manipulating the ESI syringe potential, it is possible to create complexes with up to five Cl atoms for sample peptides when the ESI is operated in the positive mode. Copyright © 2015 John Wiley & Sons, Ltd.     

Improved ion optics for introduction of ions into a 9.4‐T Fourier transform ion cyclotron resonance mass spectrometer

Enhancements to the ion source and transfer optics of our 9.4 T Fourier transform ion cyclotron resonance (ICR) mass spectrometer have resulted in improved ion transmission efficiency for more sensitive mass measurement of complex mixtures at the MS and MS/MS levels. The tube lens/skimmer has been replaced by a dual ion funnel and the following octopole by a quadrupole for reduced ion cloud radial expansion before transmission into a mass‐selective quadrupole. The number of ions that reach the ICR cell is increased by an order of magnitude for the funnel/quadrupole relative to the tube lens/skimmer/octopole. Copyright © 2015 John Wiley & Sons, Ltd.     

Monometallic cyanide cluster fullerene YCN@C78: A theoretical prediction

Stimulated by the recent experimental success in production and characterization of YCN@C_s(6)‐C₈₂, the possibility of encapsulating YCN cluster in the C₇₈ fullerene has been performed using density functional theory. Six isomers of YCN@C₇₈ are considered based on six lowest energy C₇₈^2? isomers. The results reveal that YCN@D_3h(24109)‐C₇₈ and YCN@C_2v(24107)‐C₇₈, both of which satisfy the isolated‐pentagon rule, present excellent thermodynamic stability with very small energy differences. Moreover, the large HOMO‐LUMO gaps (1.55 and 1.47 eV for YCN@D_3h(24109)‐C₇₈ and YCN@C_2v(24107)‐C₇₈, respectively) indicate their high kinetic stabilities. Significantly, in both the structures, the encapsulated YCN cluster is triangular, similar to the cases of YCN@C_s(6)‐C₈₂ and TbCN@C₂(5)‐C₈₂. In addition, electronic absorption spectra, infrared spectra, and ¹³C nuclear magnetic resonance spectra of two stable structures have also been explored to further disclose the molecular structures and properties. © 2015 Wiley Periodicals, Inc.     

Pretreating near infrared spectra with fractional order Savitzky–Golay differentiation(FOSGD)

With the aid of Riemann–Liouville fractional calculus theory,fractional order Savitzky–Golay differentiation(FOSGD) is calculated and applied to pretreat near infrared(NIR) spectra in order to improve the performance of multivariate calibrations.Similar to integral order Savitzky–Golay differentiation(IOSGD),FOSGD is obtained by fitting a spectral curve in a moving window with a polynomial function to estimate its coefficients and then carrying out the weighted average of the spectral curve in the window with the coefficients.Three NIR datasets including diesel,wheat and corn datasets were utilized to test this method.The results showed that FOSGD,which is easy to compute,is a general method to obtain Savitzky–Golay smoothing,fractional order and integral order differentiations.Fractional order differentiation computation to the NIR spectra often improves the performance of the PLS model with smaller RMSECV and RMSEP than integral order ones,especially for physical properties of interest,such as density,cetane number and hardness.     

A Near-Infrared Dye That Undergoes Multiple Interconversions through Acid–Base Equilibrium and Reversible Redox Processes

A near-infrared (NIR) polymethine dye ( 1 ), consisting of a cyclohepta[1,2-b;4,3-b′]dithiophene and two phenol moieties, was synthesized. This dye exhibited pH-responsive changes in its photophysical properties due to a two-step acid–base equilibrium that produced a protonated cation ( 1H⁺ ) and an anion ( 1⁻ ). While 1H⁺ showed an intense fluorescence in the red region of the visible spectrum, 1⁻ exhibited a strong absorption in the NIR region. The tropylium ion character in 1H⁺ induces high pK_a1 and pK_a2 values for 1 . Moreover, a stable radical ( 1^. ) was prepared, which showed a NIR absorption band with a maximum at circa 1600 nm. The cyclic voltammogram of 1^. revealed a two-step reversible redox process that produced 1⁻ and the cation 1⁺ , which is different from 1H⁺ . These redox processes accompany drastic electrochromic changes in the vis–NIR region. Overall, 1 is susceptible to multiple interconversions between five forms, due to the multifaceted character of the cycloheptadithiophene skeleton.     

Synthesis of N,N‐Dialkylamino‐nor‐Dihydroxanthene‐Hemicyanine Fused Near‐Infrared Fluorophores and Their First Water‐Soluble and/or Bioconjugatable Analogues

The effective synthesis of extended conjugated N ,N ‐dialkylamino‐nor ‐dihydroxanthene‐based fluorophores is described from diversely functionalized salicylic aldehydes. The access to these original fluorescent derivatives proceeded in two steps through a one‐pot construction of the unusual nor ‐dihydroxanthene (nor ‐DHX) scaffold followed by a diversification step providing a wide variety of nor ‐DHX‐hemicyanine fused dyes emitting in the range of 730–790 nm. The versatility of our approach has enabled a further extension to the late‐stage introduction of negatively/positively charged polar groups onto their terminal nitrogen heterocyclic subunit, thereby giving access to the first water‐soluble and/or bioconjugatable members of this emerging class of NIR fluorophores. Our water‐solubilizing method is easily implementable, and the nor ‐DHX‐hemicyanine skeleton maintains satisfying fluorescence quantum yields (5–20 %) under physiological conditions. Finally, the bioconjugation ability of fluorescent derivatives bearing a free carboxylic acid was demonstrated through the covalent labeling of a model protein, namely, bovine serum albumin.